Dispersant-viscosity improvers for lubricating oil and fuels

ABSTRACT

Hydrocarbyl substituted carboxylic compositions and derivatives thereof useful as dispersant/viscosity improvers for lubricating oil and fuel compositions. Carboxylic compositions are derived from (A) a hydrocarbon polymer having M n  ranging from about 20,000 to about 500,000, and (B) an α,β-unsaturated carboxylic compound prepared by reacting (1) an active methylene compound of the formula (I), and (2) a carbonyl compound of the general formula (H), wherein R a  is H or hydrocarbyl and R b  is a member of the group consisting of H, hydrocarbyl and (III), wherein each R′ is independently R or OR and each R is, independently, H or a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals and hemiketals of the carbonyl compound (2). Carboxylic derivative compositions are obtained by reacting the carboxylic compositions with a reactant selected from the group consisting of (a) amines characterized by the presence within their structure of at least one condensable H—N&lt;group, (b;) alcohols, (c) reactive metal or reactive metal compounds, and (d) a combination of two or more of any of (a) through (c), the components of (d) being reacted with the carboxylic composition simultaneously or sequentially, in any order.

FIELD OF THE INVENTION

[0001] This invention relates to hydrocarbyl substituted carboxyliccompositions and derivatives prepared therefrom. The carboxyliccompositions and derivatives are useful as dispersant/viscosityimprovers for lubricating oil and fuel compositions.

BACKGROUND OF THE INVENTION

[0002] The viscosity of lubricating oils, particularly the viscosity ofmineral oil based lubricating oils, is generally dependent upontemperature. As the temperature of the oil is increased, the viscosityusually decreases.

[0003] The function of a viscosity improver is to reduce the extent ofthe decrease in viscosity as the temperature is raised or to reduce theextent of the increase in viscosity as the temperature is lowered, orboth. Thus, a viscosity improver ameliorates the change of viscosity ofan oil containing it with changes in temperature. The fluiditycharacteristics of the oil are improved.

[0004] Numerous types of additives are used to improve lubricating oiland fuel compositions. Such additives include, but are not limited todispersants and detergents of the ashless and ash-containing variety,oxidation inhibitors, anti-wear additives, friction modifiers, and thelike. Such materials are well known in the art and are described in manypublications, for example, Smalheer, et al, “Lubricant Additives”,Lezius-Hiles Co., Cleveland, Ohio, USA (1967); M. W. Ranney, Ed.,“Lubricant Additives”, Noyes Data Corp., Park Ridge, N.J., USA (1973);M. J. Satriana, Ed., “Synthetic Oils and Lubricant Additives, Advancessince 1977”, Noyes Data Corp., Park Ridge N.J., USA (1982), W. C.Gergel, “Lubricant Additive Chemistry”, Publication 694-320-65R1 of theLubrizol Corp., Wickliffe, Ohio, USA (1994); and W. C. Gergel et al,“Lubrication Theory and Practice” Publication 794-320-59R3 of theLubrizol Corp., Wickliffe, Ohio, USA (1994); and in numerous UnitedStates patents, for example Chamberlin, III, U.S. Pat. No. 4,326,972,Ripple et al, U.S. Pat. No. 4,904,401, and Ripple et al, U.S. Pat. No.4,981,602.

[0005] Dispersants are well-known in the lubricating art. Dispersantsare employed in lubricants to keep impurities, particularly those formedduring operation of mechanical devices such as internal combustionengines, automatic transmissions, etc. in suspension rather thanallowing them to deposit as sludge or other deposits on the surfaces oflubricated parts.

[0006] Conventional dispersants are poor contributors to improving hightemperature, e.g., 100° C., viscosity. Mixtures of conventionaldispersants with polymeric viscosity improvers are often used but suchcombinations are costly and may adversely affect low temperatureviscometric performance.

[0007] Multifunctional additives that provide both viscosity improvingproperties and dispersant properties are likewise known in the art. Suchproducts are described in numerous publications including DieterKlamann, “Lubricants and Related Products”, Verlag Chemie Gmbh (1984),pp. 185-193; C. V. Smalheer and R. K. Smith, “Lubricant Additives”,Lezius-Hiles Co. (1967); M. W. Ranney, “Lubricant Additives”, Noyes DataCorp. (1973), pp. 92-145, M. W. Ranney, “Lubricant Additives, RecentDevelopments”, Noyes Data Corp. (1978), pp. 139-164; and M. W. Ranney,“Synthetic Oils and Additives for Lubricants”, Noyes Data Corp. (1980),pp. 96-166. Each of these publications is hereby expressly incorporatedherein by reference.

[0008] Dispersant-viscosity improvers are generally prepared byfunctionalizing, i.e., adding polar groups, to a hydrocarbon polymer.

[0009] Hayashi et al, U.S. Pat. No. 4,670,173 relates to compositionssuitable for use as dispersant-viscosity improvers made by reacting anacylating reaction product which is formed by reacting a hydrogenatedblock copolymer and an alpha,beta olefinically unsaturated reagent inthe presence of free-radical initiators, then reacting the acylatingproduct with a primary amine and optionally with a polyamine and amono-functional acid.

[0010] Chung et al, U.S. Pat. No. 5,035,821 relates to viscosity indeximprover-dispersants comprised of the reaction products of an ethylenecopolymer grafted with ethylenically unsaturated carboxylic acidmoieties, a polyamine having two or more primary amino groups or polyoland a high functionality long chain hydrocarbyl substituted dicarboxylicacid or anhydride.

[0011] Van Zon et al, U.S. Pat. No. 5,049,294, relates to dispersant/VIimprovers produced by reacting an alpha,beta-unsaturated carboxylic acidwith a selectively hydrogenated star-shaped polymer then reacting theproduct so formed with a long chain alkane-substituted carboxylic acidand with a C₁ to C₁₈ amine containing 1 to 8 nitrogen atoms and/or withan alkane polyol having at least two hydroxy groups or with thepreformed product thereof.

[0012] Bloch et al, U.S. Pat. No. 4,517,104, relates to oil solubleviscosity improving ethylene copolymers reacted or grafted withethylenically unsaturated carboxylic acid moieties then with polyamineshaving two or more primary amine groups and a carboxylic acid componentor the preformed reaction product thereof.

[0013] Gutierrez et al, U.S. Pat. No. 4,632,769, describes oil-solubleviscosity improving ethylene copolymers reacted or grafted withethylenically unsaturated carboxylic acid moieties and reacted withpolyamines having two or more primary amine groups and a C₂₂ to C₂₈olefin carboxylic acid component.

[0014] Lange, et al, U.S. Pat. No. 4,491,527 relates toester-heterocycle compositions useful as “lead paint” inhibitors inlubricants. The compositions comprise derivatives of substitutedcarboxylic acids in which the substituent is a substantially aliphatic,substantially saturated hydrocarbon based radical containing at leastabout 30 aliphatic carbon atoms; said derivatives being the combinationof: (A) at least one ester of said carboxylic acids in which all thealcohol moieties are derived from at least on mono- orpolyhydroxyalkane; and (B) at least one heterocyclic condensationproduct of said substituted carboxylic acids containing at least oneheterocyclic moiety which includes a 5- or 6-membered ring whichcontains at least two ring hetero atoms selected from the groupconsisting of oxygen, sulfur and nitrogen separated by a single carbonatom, at least one of said hetero atoms being nitrogen, and at least onecarboxylic moiety; the carboxylic and heterocyclic moieties either beinglinked through an ester or amide linkage or being the same moiety inwhich said single carbon atom separating two ring hetero atomscorresponds to a carbonyl carbon atom of the substituted carboxylicacid.

[0015] Lange, et al, U.S. Pat. No. 5,512,192 teach dispersant viscosityimprovers for lubricating oil compositions comprising a vinylsubstituted aromatic-aliphatic conjugated diene block copolymer graftedwith an ethylenically unsaturated carboxylic acid reacted with at leastone polyester containing at least one condensable hydroxy group and atleast one polyamine having at least one condensable primary or secondaryamino group, and optionally, at least one hydrocarbyl substitutedcarboxylic acid or anhydride.

[0016] Lange, U.S. Pat. No. 5,540,851 describes dispersant viscosityimprovers for lubricating oil compositions which are the reactionproduct of (a) an oil soluble ethylene-alpha olefin copolymer whereinthe alpha olefin is selected from the group consisting of C₃₋₂₈ alphaolefins, said polymer having a number average molecular weight rangingfrom about 30,000 to about 300,000 grafted with an ethylenicallyunsaturated carboxylic acid or functional derivative thereof; with atleast one polyester containing at least one condensable hydroxyl group,and at least one polyamine having at least one condensable primary orsecondary amino group, and optionally at least one hydrocarbylsubstituted carboxylic acid or anhydride.

[0017] Each of these patents is hereby expressly incorporated herein byreference.

[0018] For additional disclosures concerning multi-purpose additives andparticularly viscosity improvers and dispersants, the disclosures of thefollowing United States patents are incorporated herein by reference:2,973,344 3,488,049 3,799,877 3,278,550 3,513,095 3,842,010 3,311,5583,563,960 3,864,098 3,312,619 3,598,738 3,864,268 3,326,804 3,615,2883,879,304 3,403,011 3,637,610 4,033,889 3,404,091 3,652,239 4,051,0483,445,389 3,687,849 4,234,435

[0019] Many such additives are derived from carboxylic reactants, forexample, acids, esters, anhydrides, lactones, and others. Specificexamples of commonly used carboxylic compounds used as intermediates forpreparing lubricating oil additives include high molecular weighthydrocarbyl group substituted carboxylic acids such as succinic acidsand anhydrides, aromatic acids, such as salicylic acids, and others.Illustrative carboxylic compounds are described in Lange et al, U.S.Pat. No. 5,512,192, Lange U.S. Pat. Nos. 5,540,851 and 5,811,378 andHayashi et al U.S. Pat. No. 4,670,173.

[0020] Such carboxylic acids are typically prepared by thermallyreacting or free radical grafting of carboxylic groups such as maleicanhydride, acrylic compounds, etc. with a high molecular weighthydrocarbon. Reaction rates are relatively low. Attempts to improve theconversion rate by increasing the reaction temperature and/or usingsuper-atmospheric pressure often results in degradation of maleicanhydride to carbon dioxide, water and tar-like solids

[0021] In industry, it is also desirable to have available a widevariety of reactants available to prepare compositions. Materialsshortages, costs, etc. contribute to uncertainties in the industry.These uncertainties can be relieved when more than a limited number oftypes raw materials are available to a manufacturer. The compositions ofthis invention are prepared employing raw materials that are differentfrom, and are not suggested by, traditionally used raw materials.

SUMMARY OF THE INVENTION

[0022] This invention relates to carboxylic compositions and derivativesthereof useful as dispersant viscosity improvers for lubricating oilsand fuels. The carboxylic compositions are also useful as intermediatesfor preparing derivatives for use as dispersant viscosity improvers.Both the carboxylic compositions and the derivatives thereof findutility as dispersant/viscosity improvers for lubricating oil and fuelcompositions. Hydrocarbyl group substituted carboxylic compositions arederived from (A) a hydrocarbon polymer having {overscore (M)}_(n)ranging from about 20,000 to about 500,000 and (B) an α,β-unsaturatedcarboxylic compound prepared by reacting (1) an active methylenecompound of the formula

[0023] and (2) a carbonyl compound of the general formula

[0024] wherein R^(a) is H or hydrocarbyl and R^(b) is a member of thegroup consisting of H, hydrocarbyl and

[0025] wherein each R′ is independently R or OR and each R is,independently, H or a hydrocarbyl group; and lower alkyl acetals,ketals, hemiacetals and hemiketals of the carbonyl compound (2).Carboxylic derivative compositions are obtained by reacting thecarboxylic compositions with a reactant selected from the groupconsisting of (a) amines characterized by the presence within theirstructure of at least one condensable H—N<group, (b) alcohols, (c)reactive metal or reactive metal compounds, and (d) a combination of twoor more of any of (a) through (c), the components of (d) being reactedwith the carboxylic composition simultaneously or sequentially, in anyorder.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] As used herein, the terms “hydrocarbon”, “hydrocarbyl” or“hydrocarbon based” mean that the group being described haspredominantly hydrocarbon character within the context of thisinvention. These include groups that are purely hydrocarbon in nature,that is, they contain only carbon and hydrogen. They may also includegroups containing substituents or atoms which do not alter thepredominantly hydrocarbon character of the group. Such substituents mayinclude halo-, alkoxy-, nitro-, etc. These groups also may containhetero atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, sulfur, nitrogen and oxygen.Therefore, while remaining predominantly hydrocarbon in character withinthe context of this invention, these groups may contain atoms other thancarbon present in a chain or ring otherwise composed of carbon atoms.

[0027] In general, no more than about three non-hydrocarbon substituentsor hetero atoms, and preferably no more than one, will be present forevery 10 carbon atoms in the hydrocarbon or hydrocarbon based groups.Most preferably, the groups are purely hydrocarbon in nature, that isthey are essentially free of atoms other than carbon and hydrogen.

[0028] Throughout the specification and claims the expression oilsoluble or dispersible is used. By oil soluble or dispersible is meantthat an amount needed to provide the desired level of activity orperformance can be incorporated by being dissolved, dispersed orsuspended in an oil of lubricating viscosity. Usually, this means thatat least about 0.001% by weight of the material can be incorporated in alubricating oil composition. For a further discussion of the terms oilsoluble and dispersible, particularly “stably dispersible”, see U.S.Pat. No. 4,320,019 which is expressly incorporated herein by referencefor relevant teachings in this regard.

[0029] It must be noted that as used in this specification and appendedclaims, the singular forms also include the plural unless the contextclearly dictates otherwise. Thus the singular forms “a”, “an”, and “the”include the plural; for example “an amine” includes mixtures of aminesof the same type. As another example the singular form “amine” isintended to include both singular and plural unless the context clearlyindicates otherwise.

[0030] Hydrocarbon Polymer

[0031] As used herein, the expression ‘polymer’ refers to polymers ofall types, i.e., homopolymers and copolymers. The term homopolymerrefers to polymers derived from essentially one monomeric species;copolymers are defined herein as being derived from 2 or more monomericspecies.

[0032] The hydrocarbon polymer is an essentially hydrocarbon basedpolymer, usually one having a number average molecular weight({overscore (M)}_(n)) between about 20,000 and about 500,000, often fromabout 20,000 to about 300,000, frequently from about 40,000 to about200,000. Molecular weights of the hydrocarbon polymer are determinedusing well known methods described in the literature. Examples ofprocedures for determining the molecular weights are gel permeationchromatography (GPC) (also known as size-exclusion chromatography) andvapor phase osmometry (VPO). It is understood that these are averagemolecular weights. GPC molecular weights are typically accurate withinabout 5-10%. Even with narrow polydispersity, a polymer with {overscore(M)}_(n) of about 20,000 may have some species as low as about 15,000. Apolymer with {overscore (M)}_(w) about 35,000 and {overscore (M)}_(n)about 20,000 may have GPC peaks corresponding to polymer components aslow as about 10,000 and as high as 75,000.

[0033] These and other procedures are described in numerous publicationsincluding:

[0034] P. J. Flory, “Principles of Polymer Chemistry”, CornellUniversity Press (1953), Chapter VII, pp. 266-316,

[0035] “Macromolecules, an Introduction to Polymer Science”, F. A. Boveyand F. H. Winslow, Editors, Academic Press (1979), pp. 296-312, and

[0036] W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size ExclusionLiquid Chromatography”, John Wiley and Sons, New York, 1979.

[0037] Unless otherwise indicated, GPC molecular weights referred toherein are polystyrene equivalent weights, i.e., are molecular weightsdetermined employing polystyrene standards.

[0038] A measurement which is complementary to a polymer's molecularweight is the melt index (ASTM D-1238). Polymers of high melt indexgenerally have low molecular weight, and vice versa. The polymers of thepresent invention preferably have a melt index of up to 20 dg/min., morepreferably 0.1 to 10 dg/min.

[0039] These publications are hereby incorporated by reference forrelevant disclosures contained therein relating to the determination ofmolecular weight.

[0040] When the molecular weight of a polymer is greater than desired,it may be reduced by techniques known in the art. Such techniquesinclude mechanical shearing of the polymer employing masticators, ballmills, roll mills, extruders and the like. Oxidative or thermal shearingor degrading techniques are also useful and are known. Details ofnumerous procedures for shearing polymers are given in U.S. Pat. No.5,348,673 which is hereby incorporated herein by reference for relevantdisclosures in this regard. Reducing molecular weight also tends toimprove the subsequent shear stability of the polymer.

[0041] The polymer may contain aliphatic, aromatic or cycloaliphaticcomponents, or mixtures thereof. When the polymer is prepared from themonomers, it may contain substantial amounts of olefinic unsaturation,oftentimes far in excess of that which is desired for this invention.The polymer may be subjected to hydrogenation to reduce the amount ofunsaturation to such an extent that the resulting hydrogenated polymerhas olefinic unsaturation, based on the total number of carbon to carbonbonds in the polymer, of less than 5%, frequently less than 2%, often nomore than 1% olefinic unsaturation.

[0042] In one embodiment, the polymer is substantially saturated. Bysubstantially saturated is meant that no more than 5% of the carbon tocarbon bonds, often no more than 1% and frequently no more than 0.5% ofthe carbon to carbon bonds are olefinically unsaturated. Most often,substantially saturated means that the polymer is essentially free ofolefinic unsaturation. In the case where the polymer is substantiallysaturated, the reaction with (B) is conducted employing a free radicalinitiator. Such processes are described in U.S. Pat. Nos. 5,512,192 and5,540,851 which are incorporated herein by reference.

[0043] In another embodiment, the polymer (A) contains olefinicunsaturation and the reaction is conducted thermally, employing the wellknown “ene” process, optionally in the presence of added chlorine. Theuse of added chlorine during the reaction often facilitates thereaction. Nonetheless, in order to avoid the presence of chlorine in thegrafted product and derivatives thereof, it is preferred to conduct thegrafting reaction thermally or in the presence of a free radicalinitiator.

[0044] The “ene” process is described in the literature, for example inU.S. Pat. No. 3,412,111 and Ben et al, “The Ene Reaction of MaleicAnhydride With Alkenes”, J. C. S Perkin II (1977), pp. 535-537, both ofwhich are incorporated herein by reference for relevant disclosurescontained therein.

[0045] Chlorine assisted grafting is described in numerous patentsincluding U.S. Pat. Nos. 3,215,707; 3,912,764; and 4,234,435, which areincorporated herein by reference.

[0046] Typically, from about 90 to about 99.9%, often 100% of carbon tocarbon bonds in the polymer are saturated. As noted, the choice ofgrafting procedure typically depends upon the extent of olefinicunsaturation present in the polymer. Free radical initiators aretypically used when the polymer is substantially saturated; the thermal“ene” process may be used when the polymer contains significant amountsof olefinic unsaturation.

[0047] Aromatic unsaturation is not considered olefinic unsaturationwithin the context of this invention. Depending on hydrogenationconditions, up to about 20% of aromatic groups may be hydrogenated;however, typically no more than about 5%, usually less than 1% ofaromatic bonds are hydrogenated. Most often, substantially none of thearomatic bonds are hydrogenated.

[0048] In one typical embodiment, the polymer contains an average offrom 1 to about 9,000 olefinic double bonds, more often from about 1 toabout 100 olefinic double bonds, even more often from about 1,frequently 2 to about 10, up to about 50, olefinic double bonds permolecule based on the {overscore (M)}_(n) of the polymer. In anotherembodiment, the polymer contains about 1 olefinic double bond for aboutevery 20, often for about every 70 to 7000 carbon atoms. In stillanother embodiment, the hydrocarbon polymer contains about 1 olefinicdouble bond for every 4,000 to 20,000 on {overscore (M)}_(n) basis,often, about 1 olefinic double bond per 1,000 to 40,000 on {overscore(M)}_(n) basis. Thus, for example, in this embodiment a polymer of{overscore (M)}_(n)=80,000 would contain from about 2 to about 80olefinic double bonds per molecule, often from about 4 to about 20double bonds per molecule. In yet another embodiment, the hydrocarbonpolymer (P) contains about 1 olefinic double bond for about every 300 to100,000 on {overscore (M)}_(n) basis.

[0049] As noted hereinabove, in another embodiment, the polymer issubstantially saturated, as defined hereinabove.

[0050] The equivalent weight per mole of carbon to carbon double bondsis defined herein as the mole-equivalent weight. For example, a polymerhaving {overscore (M)}_(n) of 100,000 and which contains an average of 4moles of carbon to carbon double bonds, has a mole equivalent weight of100,000/4=25,000. Conversely, the polymer has one mole of carbon tocarbon double bonds per 25,000 {overscore (M)}_(n).

[0051] In preferred embodiments, the hydrocarbon polymer is at least oneoil soluble or dispersible homopolymer or copolymer selected from thegroup consisting of:

[0052] (1) polymers of dienes;

[0053] (2) copolymers of conjugated dienes with vinyl substitutedaromatic compounds;

[0054] (3) polymers of aliphatic olefins having from 2 to about 28carbon atoms;

[0055] (4) olefin-diene copolymers; and

[0056] (5) star polymers.

[0057] These preferred polymers are described in greater detailhereinbelow.

[0058] (1) Polymers of Dienes

[0059] The hydrocarbon polymer may be a homopolymer or copolymer of oneor more dienes. The dienes may be conjugated such as isoprene, butadieneand piperylene or non-conjugated such as 1-4 hexadiene, ethylidenenorbornene, vinyl norbornene, 4-vinyl cyclohexene, anddicyclopentadiene. Polymers of conjugated dienes are preferred. Suchpolymers are conveniently prepared via free radical and anionicpolymerization techniques. Emulsion techniques are commonly employed forfree radical polymerization.

[0060] As noted hereinabove, useful polymers have {overscore (M)}_(n)ranging from about 20,000 to about 500,000. More often, useful polymersof this type have {overscore (M)}_(n) ranging from about 50,000 to about150,000.

[0061] These polymers may be and often are hydrogenated to reduce theamount of olefinic unsaturation present in the polymer. They may or maynot be exhaustively hydrogenated. Hydrogenation is often accomplishedemploying catalytic methods. Catalytic techniques employing hydrogenunder high pressure and at elevated temperature are well-known to thoseskilled in the chemical art. Other methods are also useful and are wellknown to those skilled in the art.

[0062] Extensive discussions of diene polymers appear in the“Encyclopedia of Polymer Science and Engineering”, Volume 2, pp. 550-586and Volume 8, pp. 499-532, Wiley-Interscience (1986), which are herebyexpressly incorporated herein by reference for relevant disclosures inthis regard.

[0063] The polymers include homopolymers and copolymers of conjugateddienes including polymers of 1,3-dienes of the formula

[0064] wherein each substituent denoted by R, or R with a numericalsubscript, is independently hydrogen or hydrocarbon based, whereinhydrocarbon based is as defined hereinabove. Preferably at least onesubstituent is H. Normally, the total carbon content of the diene willnot exceed 20 carbons. Preferred dienes for preparation of the polymerare piperylene, isoprene, 2,3-dimethyl-1,3-butadiene, chloroprene and1,3-butadiene.

[0065] Suitable homopolymers of conjugated dienes are described, andmethods for their preparation are given in numerous U.S. patents,including the following:

[0066] U.S. Pat. No. 3,547,821

[0067] U.S. Pat. No. 3,835,053

[0068] U.S. Pat. No. 3,959,161

[0069] U.S. Pat. No. 3,965,019

[0070] U.S. Pat. No. 4,085,055

[0071] U.S. Pat. No. 4,116,917

[0072] As a specific example, U.S. Pat. No. 3,959,161 teaches thepreparation of hydrogenated polybutadiene. In another example, uponhydrogenation, 1,4-polyisoprene becomes an alternating copolymer ofethylene and propylene.

[0073] Copolymers of conjugated dienes are prepared from two or moreconjugated dienes. Useful dienes are the same as those described in thepreparation of homopolymers of conjugated dienes hereinabove. Thefollowing U.S. patents describe diene copolymers and methods forpreparing them:

[0074] U.S. Pat. No. 3,965,019

[0075] U.S. Pat. No. 4,073,737

[0076] U.S. Pat. No. 4,085,055

[0077] U.S. Pat. No. 4,116,917

[0078] For example, U.S. Pat. No. 4,073,737 describes the preparationand hydrogenation of butadiene-isoprene copolymers.

[0079] (2) Copolymers of Conjugated Dienes with Vinyl SubstitutedAromatic Compounds

[0080] In one embodiment, the hydrocarbon polymer is a copolymer of avinyl-substituted aromatic compound and a conjugated diene. The vinylsubstituted aromatics generally contain from 8 to about 20 carbons,preferably from 8 to 12 carbon atoms and most preferably, 8 or 9 carbonatoms.

[0081] Examples of vinyl-substituted aromatics include vinylanthracenes, vinyl naphthalenes and vinyl benzenes (styrenic compounds).Styrenic compounds are preferred, examples being styrene,alpha-methystyrene, ortho-methyl styrene, meta-methyl styrene,para-methyl styrene, para-tertiary-butylstyrene and chlorostyrene, withstyrene being preferred.

[0082] The conjugated dienes generally have from 4 to about 10 carbonatoms and preferably from 4 to 6 carbon atoms. Example of conjugateddienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene,isoprene and 1,3-butadiene, with isoprene and 1,3-butadiene beingparticularly preferred. Mixtures of such conjugated dienes are useful.

[0083] The vinyl substituted aromatic content of these copolymers istypically in the range of about 20% to about 70% by weight, preferablyabout 40% to about 60% by weight. The aliphatic conjugated diene contentof these copolymers is typically in the range of about 30% to about 80%by weight, preferably about 40% to about 60% by weight.

[0084] The polymers, and in particular, styrene-diene copolymers, can berandom copolymers or block copolymers, which include regular blockcopolymers or random block copolymers. Random copolymers are those inwhich the comonomers are randomly, or nearly randomly, arranged in thepolymer chain with no significant blocking of homopolymer of eithermonomer. Regular block copolymers are those in which a small number ofrelatively long chains of homopolymer of one type of monomer arealternately joined to a small number of relatively long chains ofhomopolymer of another type of monomer. Random block copolymers arethose in which a larger number of relatively short segments ofhomopolymer of one type of monomer alternate with relatively shortsegments of homopolymer of another monomer.

[0085] The random, regular block and random block polymers used in thisinvention may be linear, or they may be partially or highly branched.The relative arrangement of homopolymer segments in a linear regularblock or random block polymer is obvious. Differences in structure liein the number and relative sizes of the homopolymer segments; thearrangement in a linear block polymer of either type is alwaysalternating in homopolymer segments.

[0086] Normal or regular block copolymers usually have from 1 to about5, often 1 to about 3, preferably only from 1 to about 2 relativelylarge homopolymer blocks of each monomer. Thus, a linear regular diblockcopolymer of styrene or other vinyl aromatic monomer (S) and diene (D)would have a general structure represented by a large block ofhomopolymer (S) attached to a large block of homopolymer (D), as:

(S)_(s)(D)_(d)

[0087] where subscripts s and d are as described hereinbelow. Similarly,a regular linear tri-block copolymer of styrene or other vinyl aromaticmonomer (S) and diene monomer (D) may be represented, for example, by

(S)_(s)(D)_(d)(S), or (D)_(d)(S)_(s)(D)_(d).

[0088] Techniques vary for the preparation of these “S-D-S” and “D-S-D”triblock polymers, and are described in the literature for anionicpolymerization.

[0089] A third monomer (T) may be incorporated into linear, regularblock copolymers. Several configurations are possible depending on howthe homopolymer segments are arranged with respect to each other. Forexample, linear triblock copolymers of monomers (S), (D) and (T) can berepresented by the general configurations:

(S)_(s)-(D)_(d)-(T)_(t), (S)_(g)-(T)_(t)-(D)_(d), or(D)_(d)-(S)_(s)-(T)_(t),

[0090] wherein the lower case letters s, d and t represent theapproximate number of monomer units in the indicated block.

[0091] The sizes of the blocks are not necessarily the same, but mayvary considerably. The only stipulation is that any regular blockcopolymer comprises relatively few, but relatively large, alternatinghomopolymer segments.

[0092] As an example, when (D) represents blocks derived from diene suchas isoprene or butadiene, “d” usually ranges from about 100 to about2000, preferably from about 500 to about 1500; when (S) represents, forexample, blocks derived from styrene, “s” usually ranges from about 100to about 2000, preferably from about 200 to about 1000; and when a thirdblock (T) is present, “t” usually ranges from about 10 to about 1000,provided that the {overscore (M)}_(n) of the polymer is within theranges indicated as useful for this invention.

[0093] The copolymers can be prepared by methods well known in the art.Such copolymers usually are prepared by anionic polymerization usingGroup Ia metals in the presence of electron-acceptor aromatics, orpreformed organometallics such as sec-butyllithium as polymerizationcatalysts.

[0094] The styrene/diene block polymers are usually made by anionicpolymerization, using a variety of techniques, and altering reactionconditions to produce the most desirable features in the resultingpolymer. In an anionic polymerization, the initiator can be either anorganometallic material such as an alkyl lithium, or the anion formed byelectron transfer from a Group Ia metal to an aromatic material such asnaphthalene. A preferred organometallic material is an alkyl lithiumsuch as sec-butyl lithium; the polymerization is initiated by additionof the butyl anion to either the diene monomer or to the styrene.

[0095] When an alkyl lithium initiator is used, a homopolymer of onemonomer, e.g., styrene, can be selectively prepared, with each polymermolecule having an anionic terminus, and lithium gegenion. Thecarbanionic terminus remains an active initiation site toward additionalmonomers. The resulting polymers, when monomer is completely depleted,will usually all be of similar molecular weight and composition, and thepolymer product will be “monodisperse” (i.e., the ratio of weightaverage molecular weight to number average molecular weight is verynearly 1.0). At this point, addition of 1,3-butadiene, isoprene or othersuitable anionically polymerizable monomer to thehomopolystyrene-lithium “living” polymer produces a second segment whichgrows from the terminal anion site to produce a living di-block polymerhaving an anionic terminus, with lithium gegenion.

[0096] Subsequent introduction of additional styrene can produce a newpoly S-block-poly D-block-poly S, or S-D-S triblock polymer; higherorders of block polymers can be made by consecutive stepwise additionsof different monomers in different sequences.

[0097] Alternatively, a living diblock polymer can be coupled byexposure to an agent such as a dialkyl dichlorosilane. When thecarbanionic “heads” of two S-D diblock living polymers are coupled usingsuch an agent, precipitation of LiCl occurs to give an S-D-S triblockpolymer.

[0098] Block copolymers made by consecutive addition of styrene to givea relatively large homopolymer segment (S), followed by a diene to givea relatively large homopolymer segment (D), are referred to aspoly-S-block-poly-D copolymers, or S-D diblock polymers.

[0099] When metal naphthalide is employed as initiator, the dianionformed by electron transfer from metal, e.g., Na, atoms to thenaphthalene ring can generate dianions which may initiatepolymerization, e.g. of monomer S, in two directions simultaneously,producing essentially a homopolymer of S having anionic termini at bothends.

[0100] Subsequent exposure of the poly (S) dianion to a second monomer(D) results in formation of a poly D-block-poly S-block-poly D, or aD-S-D triblock polymeric dianion, which may continue to interact withadditional anionically-polymerizable monomers of the same, or differentchemical type, in the formation of higher order block polymers. Ordinaryblock copolymers are generally considered to have up to about 5 suchblocks.

[0101] Usually, one monomer or another in a mixture will polymerizefaster, leading to a segment that is richer in that monomer, interruptedby occasional incorporation of the other monomer. This can be used tobuild a type of polymer referred to as a “random block polymer”, or“tapered block polymer”. When a mixture of two different monomers isanionically polymerized in a non-polar paraffinic solvent, one willinitiate selectively, and usually polymerize to produce a relativelyshort segment of homopolymer. Incorporation of the second monomer isinevitable, and this produces a short segment of different structure.Incorporation of the first monomer type then produces another shortsegment of that homopolymer, and the process continues, to give a“random” alternating distribution of relatively short segments ofhomopolymers, of different lengths. Random block polymers are generallyconsidered to be those comprising more than 5 such blocks. At somepoint, one monomer will become depleted, favoring incorporation of theother, leading to ever longer blocks of homopolymer, resulting in a“tapered block copolymer.”

[0102] An alternative way of preparing random or tapered blockcopolymers involves initiation of styrene, and interrupting withperiodic, or step, additions of diene monomer. The additions areprogrammed according to the relative reactivity ratios and rateconstants of the styrene and particular diene monomer.

[0103] “Promoters” are electron-rich molecules that facilitate anionicinitiation and polymerization rates while lessening the relativedifferences in rates between various monomers. Promoters also influencethe way in which diene monomers are incorporated into the block polymer,favoring 1,2-polymerization of dienes over the normal 1,4-cis-addition.

[0104] These polymers may have considerable olefinic unsaturation, whichmay be reduced, if desired. Hydrogenation to reduce the extent ofolefinic unsaturation may be carried out to reduce approximately90-99.1% of the olefinic unsaturation of the initial polymer, such thatfrom about 90 to about 99.9% of the carbon to carbon bonds of thepolymer are saturated. In general, it is preferred that these copolymerscontain no more than about 10%, preferably no more than 5% and often nomore than about 0.5% residual olefinic unsaturation on the basis of thetotal amount of olefinic double bonds present in the polymer prior tohydrogenation. Unsaturation can be measured by a number of means wellknown to those of skill in the art, including infrared, nuclear magneticresonance spectroscopy, bromine number; iodine number, and other means.Aromatic unsaturation is not considered to be olefinic unsaturationwithin the context of this invention.

[0105] Hydrogenation techniques are well known to those of skill in theart. One common method is to contact the copolymers with, hydrogen,often at superatmospheric pressure in the presence of a metal catalystsuch as colloidal nickel, palladium supported on charcoal, etc.Hydrogenation may be carried out as part of the overall productionprocess, using finely divided, or supported, nickel catalyst. Othertransition metals may also be used to effect the transformation. Othertechniques are known in the art.

[0106] Other polymerization techniques such as emulsion polymerizationcan be used.

[0107] Often the arrangement of the various homopolymer blocks isdictated by the reaction conditions such as catalyst and polymerizationcharacteristics of the monomers employed. Conditions for modifyingarrangement of polymer blocks are well known to those of skill in thepolymer art. Literature references relating to polymerization techniquesand methods for preparing certain types of block polymers include:

[0108] 1) “Encyclopedia of Polymer Science and Engineering”,Wiley-Interscience Publishing, New York, (1986);

[0109] 2) A. Noshay and J. E. McGrath, “Block Copolymers”, AcademicPress, New York, (1977);

[0110] 3) R. J. Ceresa, ed., “Block and Graft Copolymerization”, JohnWiley and Sons, New York, (1976); and

[0111] 4) D. J. Meier, ed., (Block Copolymers”, MMI Press, HarwoodAcademic Publishers, New York, (1979).

[0112] Each of these is hereby incorporated herein by reference forrelevant disclosures relating to block copolymers.

[0113] Examples of suitable commercially available regular lineardiblock copolymers as set forth above include SHELLVIS®-40, andSHELLVIS®-50, both hydrogenated styrene-isoprene block copolymers,manufactured by Shell Chemical.

[0114] Examples of commercially available random block and tapered blockcopolymers include the various GLISSOVISCAL® styrene-butadienecopolymers manufactured by BASF. A previously available random blockcopolymer was PHIL-AD® viscosity improver, manufactured by PhillipsPetroleum.

[0115] The copolymers preferably have {overscore (M)}_(n) in the rangeof about 20,000 to about 500,000, more preferably from about 30,000 toabout 150,000. The weight average molecular weight ({overscore (M)}_(w))for these copolymers is generally in the range of about 50,000 to about500,000, preferably from about 50,000 to about 300,000.

[0116] Copolymers of conjugated dienes with olefins containing aromaticgroups, e.g., styrene, methyl styrene, etc. are described in numerouspatents including the following: 3,554,911 4,082,680 3,992,310 4,085,0553,994,815 4,116,917 4,031,020 4,136,048 4,073,738 4,145,298 4,077,893

[0117] For example, U.S. Pat. No. 3,554,911 describes a randombutadiene-styrene copolymer, its preparation and hydrogenation.

[0118] (3) Polymers of Aliphatic Olefins

[0119] Another useful hydrocarbon polymer is one which in its main chainis composed essentially of aliphatic olefin, especially alpha olefin,monomers. The polyolefins of this embodiment thus exclude polymers whichhave a large component of other types of monomers copolymerized in themain polymer, such as ester monomers, acid monomers, and the like. Thepolyolefin may contain impurity amounts of such materials, e.g., lessthan 5% by weight, more often less than 1% by weight, preferably, lessthan 0.1% by weight of other monomers. Useful polymers include oilsoluble or dispersible polymers of alpha-olefins.

[0120] The olefin copolymer preferably has a number average molecularweight ({overscore (M)}_(n)) determined by gel-permeation chromatographyemploying polystyrene standards, ranging from about 20,000 to about500,000, often from about 30,000 to about 300,000, often to about200,000, more often from about 50,000 to about 150,000, even more oftenfrom about 80,000 to about 150,000. Exemplary polydispersity values({overscore (M)}_(w)/{overscore (M)}_(n)) range from about 1.5 to about3.5, often to about 3.0, preferably, from about 1.7, often from about2.0, to about 2.5.

[0121] These polymers may be homopolymers or copolymers and arepreferably polymers of alpha-olefins having from 2 to about 28 carbonatoms. Preferably they are copolymers, more preferably copolymers ofethylene and at least one other α-olefin having from 3 to about 28carbon atoms, i.e., one of the formula CH₂═CHR₁ wherein R₁ is straightchain or branched chain allyl radical comprising 1 to 26 carbon atoms.Preferably R₁ is alkyl of from 1 to 8 carbon atoms, and more preferablyis alkyl of from 1 to 2 carbon atoms. Examples include homopolymers frommonoolefins such as propylene, 1-butene, isobutene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc andcopolymers, preferably of ethylene with one or more of these monomers.Preferably, the polymer of olefins is an ethylene-propylene copolymer.

[0122] The ethylene content is preferably in the range of 20 to 80percent by weight, and more preferably 30 to 70 percent by weight. Whenpropylene and/or 1-butene are employed as comonomer(s) with ethylene,the ethylene content of such copolymers most preferably is 45 to 65percent, although higher or lower ethylene contents may be present. Mostpreferably, these polymers are substantially free of ethylenehomopolymer, although they may exhibit a degree of crystallinity due tothe presence of small crystalline polyethylene segments within theirmicrostructure.

[0123] In one particular embodiment, the polymer is a homopolymerderived from a butene, particularly, isobutylene. Especially preferredis where the polymer comprises terminal vinylidene olefinic doublebonds.

[0124] The polymers employed in this embodiment may generally beprepared substantially in accordance with procedures which are wellknown in the art.

[0125] Catalysts employed in the production of the reactant polymers arelikewise well known. One broad class of catalysts particularly suitablefor polymerization of α-olefins, comprises coordination catalysts suchas Ziegler or Ziegler-Natta catalysts comprising a transition metalatom. Ziegler-Natta catalysts are composed of a combination of atransition metal atom with an organo aluminum halide and may be usedwith additional complexing agents.

[0126] Other useful polymerization catalysts are the metallocenecompounds. These are organometallic coordination compounds obtained ascyclopentadienyl derivatives of a transition metal or metal halide. Themetal is bonded to the cyclopentadienyl ring by electrons moving inorbitals extending above and below the plane of the ring (π bond). Theuse of such materials as catalysts for the preparation of ethylene-alphaolefin copolymers is described in U.S. Pat. No. 5,446,221. The proceduredescribed therein provides ethylene-alpha olefin copolymers having atleast 30% of terminal ethenylidene unsaturation. This patent is herebyincorporated herein by reference for relevant disclosures.

[0127] Polymerization using coordination catalysis is generallyconducted at temperatures ranging between 200 and 300° C., preferablybetween 30° and 200° C. Reaction time is not critical and may vary fromseveral hours or more to several minutes or less, depending upon factorssuch as reaction temperature, the monomers to be copolymerized, and thelike. One of ordinary skill in the art may readily obtain the optimumreaction time for a given set of reaction parameters by routineexperimentation. Preferably, the polymerization will generally becompleted at a pressure of 1 to 40 MPa (10 to 400 bar).

[0128] The polymerization may be conducted employing liquid monomer,such as liquid propylene, or mixtures of liquid monomers (such asmixtures of liquid propylene and 1-butene), as the reaction medium.Alternatively, polymerization may be accomplished in the presence of ahydrocarbon inert to the polymerization such as butane, pentane,isopentane, hexane, isooctane, decane, toluene, xylene, and the like.

[0129] When carrying out the polymerization in a batch-type fashion, thereaction diluent (if any) and the alpha-olefin comonomer(s) are chargedat appropriate ratios to a suitable reactor. Care should be taken thatall ingredients are dry, with the reactants typically being passedthrough molecular sieves or other drying means prior to theirintroduction into the reactor. Subsequently, component(s) of thecatalyst are introduced while agitating the reaction mixture, therebycausing polymerization to commence. Alternatively, component(s) of thecatalyst may be premixed in a solvent and then fed to the reactor. Aspolymer is being formed, additional monomers may be added to thereactor. Upon completion of the reaction, unreacted monomer and solventare either flashed or distilled off, if necessary by vacuum, and thecopolymer withdrawn from the reactor.

[0130] The polymerization may be conducted in a continuous manner bysimultaneously feeding the reaction diluent (if employed), monomers,component(s) of the catalyst to a reactor and withdrawing solvent,unreacted monomer and polymer from the reactor so as to allow aresidence time of ingredients long enough for forming polymer of thedesired molecular weight; and separating the polymer from the reactionmixture.

[0131] In those situations wherein the molecular weight of the polymerproduct that would be produced at a given set of operating conditions ishigher than desired, any of the techniques known in the prior art forcontrol of molecular weight, such as polymerization temperature control,may be used.

[0132] The polymers are preferably formed in the substantial absence ofadded H₂ gas, that is, H₂ gas added in amounts effective tosubstantially reduce the polymer molecular weight.

[0133] The polymers can be random copolymers, block copolymers, andrandom block copolymers. Ethylene propylene copolymers are usuallyrandom copolymers. Block copolymers may be obtained by conducting thereaction in a tubular reactor. Such a procedure is described in U.S.Pat. No. 4,804,794 which is hereby incorporated by reference forrelevant disclosures in this regard.

[0134] Numerous United States patents, including the following, describethe preparation of copolymers of alpha olefins. 3,513,096 4,068,0573,551,336 4,081,391 3,562,160 4,089,794 3,607,749 4,098,710 3,634,2494,113,636 3,637,503 4,132,661 3,992,310 4,137,185 4,031,020 4,138,3704,068,056 4,144,181

[0135] Copolymers of ethylene with higher alpha olefins are the mostcommon copolymers of aliphatic olefins. Ethylene-propylene copolymersare the most common ethylene-alpha-olefin copolymers and are preferredfor use in this invention. A description of an ethylene-propylenecopolymer appears in U.S. Pat. No. 4,137,185 which is herebyincorporated herein by reference.

[0136] Useful ethylene-alpha olefin, usually ethylene-propylene,copolymers are commercially available from numerous sources includingthe Exxon, Texaco and Lubrizol Corporations.

[0137] (4) Olefin-Diene Copolymers

[0138] Another useful hydrocarbon polymer is one derived from olefins,especially lower olefins, and dienes. Preferred olefins are alphaolefins. Dienes may be non-conjugated or conjugated, usuallynon-conjugated. Useful olefins and dienes are the same as thosedescribed hereinabove and hereinafter in discussions of other polymertypes.

[0139] In one embodiment, the copolymer is an ethylene-lowerolefin-diene copolymer. As used herein, the term lower refers to groupsor compounds containing no more than 7 carbon atoms. Preferably, thediene is non-conjugated. Especially preferred areethylene-propylene-diene copolymers.

[0140] These copolymers most often will have {overscore (M)}_(n) rangingfrom about 20,000 to about 500,000, preferably from about 50,000 toabout 200,000. In another embodiment, the {overscore (M)}_(n) rangesfrom about 70,000 to about 350,000. These polymers often have arelatively narrow range of molecular weight as represented by thepolydispersity value {overscore (M)}_(n)/{overscore (M)}_(n). Typically,the polydispersity values are less than 10, more often less than 6, andpreferably less than 4, often between 2 and 3.

[0141] There are numerous commercial sources for lower olefin-dienecopolymers. For example, ORTHOLEUM® 2052 (a product marketed by theDuPont Company) which is a terpolymer having an ethylene:propyleneweight ratio of about 57:43 and containing 4-5 weight % of groupsderived from 1,4-hexadiene monomer. Other commercially availableolefin-diene copolymers including ethylene-propylene copolymers withethylidene norbornene, with dicyclopentadiene, with vinyl norbornene,with piperylene (1,3-pentadiene), with 4-vinyl cyclohexene, and numerousother such materials are readily available. Olefin-diene copolymers andmethods for their preparation are described in numerous patentsincluding the following U.S. patents:

[0142] U.S. Pat. No. 3,291,780

[0143] U.S. Pat. No. 3,300,459

[0144] U.S. Pat. No. 3,598,738

[0145] U.S. Pat. No. 4,026,809

[0146] U.S. Pat. No. 4,032,700

[0147] U.S. Pat. No. 4,156,061

[0148] U.S. Pat. No. 3,320,019

[0149] U.S. Pat. No. 4,357,250

[0150] U.S. Pat. No. 3,598,738, which describes the preparation ofethylene-propylene-1,4-hexadiene terpolymers, is illustrative. Thispatent also lists numerous references describing the use of variouspolymerization catalysts.

[0151] Another useful polymer is an olefin-conjugated diene copolymer.An example of such a polymer is butyl rubber, an isobutylene-isoprenecopolymer.

[0152] Details of various types of polymers, reaction conditions,physical properties, and the like are provided in the above patents andin numerous books, including:

[0153] “Riegel's Handbook of Industrial Chemistry”, 7th edition, JamesA. Kent Ed., Van Nostrand Reinhold Co., New York (1974), Chapters 9 and10,

[0154] P. J. Flory, “Principles of Polymer Chemistry”, CornellUniversity Press, Ithaca, N.Y. (1953),

[0155] “Kirk-Othmer Encyclopedia of Chemical Technology”, 3rd edition,Vol. 8 (Elastomers, Synthetic, and various subheadings thereunder), JohnWiley and Sons, New York (1979).

[0156] Each of the above-mentioned books and patents is hereby expresslyincorporated herein by reference for relevant disclosures containedtherein.

[0157] Polymerization can also be effected using free radical initiatorsin a well-known process, generally employing higher pressures than usedwith coordination catalysts. These polymers may be and frequently arehydrogenated to bring unsaturation to desired levels. As noted,hydrogenation may take place before or after reaction with thecarboxylic reactant.

[0158] (5) Star Polymer

[0159] Star polymers are polymers comprising a nucleus and polymericarms. Common nuclei include polyalkenyl compounds, usually compoundshaving at least two non-conjugated alkenyl groups, usually groupsattached to electron withdrawing groups, e.g., aromatic nuclei. Thepolymeric arms are often homopolymers and copolymers of dienes,preferably conjugated dienes, vinyl substituted aromatic compounds suchas monoalkenyl arenes, homopolymers of olefins such as butenes,especially isobutene, and mixtures thereof.

[0160] Molecular weights (GPC peak) of useful star polymers range fromabout 20,000, often from about 50,000 to about 500,000. They frequentlyhave {overscore (M)}_(n) ranging from about 100,000 to about 250,000.

[0161] The polymers thus comprise a poly(polyalkenyl coupling agent)nucleus with polymeric arms extending outward therefrom. The starpolymers are usually hydrogenated such that at least 80% of the olefiniccarbon-carbon bonds are saturated, more often at least 90% and even morepreferably, at least 95% are saturated. As noted herein, the polymerscontain olefrnic unsaturation; accordingly, they are not exhaustivelysaturated before reaction with the carboxylic reactant.

[0162] The polyvinyl compounds making up the nucleus are illustrated bypolyalkenyl arenes, e.g., divinyl benzene and poly vinyl aliphaticcompounds.

[0163] Dienes making up the polymeric arms are illustrated by butadiene,isoprene and the like. Monoalkenyl compounds include, for example,styrene and alkylated derivatives thereof. In one embodiment, the armsare derived from dienes. In another embodiment, the arms are derivedfrom dienes and vinyl substituted aromatic compounds. In yet anotherembodiment, the arms comprise polyisobutylene groups, often,isobutylene-conjugated diene copolymers. Arms derived from dienes orfrom dienes and vinyl substituted aromatic compounds are frequentlysubstantially hydrogenated.

[0164] Star polymers are well known in the art. Such material andmethods for preparing same are described in numerous publications andpatents, including the following United States patents which are herebyincorporated herein by reference for relevant disclosures containedtherein:

[0165] U.S. Pat. No. 4,116,917,

[0166] U.S. Pat. No. 4,141,847,

[0167] U.S. Pat. No. 4,346,193,

[0168] U.S. Pat. No. 4,358,565,

[0169] and U.S. Pat. No. 4,409,120.

[0170] Star polymers are commercially available, for example as Shellvis200 sold by Shell Chemical Co.

[0171] Mixtures of two or more hydrocarbon polymers may be used.

[0172] α,β-Unsaturated Carboxylic Compound

[0173] The α,β-unsaturated carboxylic compound used in the preparationof the hydrocarbyl substituted carboxylic compositions of this inventionare themselves prepared by reacting (1) an active methylene compound and(2) a carbonyl compound as described in detail herein. They arepreferably polycarboxylic compounds of the general formula

[0174] wherein R^(c) is R;

[0175] or —CHO;

[0176] and each R is, independently, H or hydrocarbyl.

[0177] With the reaction of dimethyl malonate and the methyl hemiacetalof methyl glyoxylate, a minor amount (ca. 5% yield) of a product havingthe formula

[0178] has been obtained.

[0179] Several compounds of this type are described in Hall et al,Polymer Bulletin 16, 405-9 (1986); Evans et al, J. Org. Chem. 54 2849(1989); Hall et al, Macromolecules 8 22, (1975); Stetter et al,Synthesis 626 (1981); Wilk, Tetrahedron 53, 7097 (1997); Hawkins et al,U.S. Pat. No. 4,049,698 and Roblin et al U.S. Pat. No. 2,293,309.

[0180] The reacting of (1) an active methylene compound and (2) acarbonyl compound take place with or without solvent and with or withoutcatalyst. Generally, the reaction takes place at temperatures betweenabout 120° C. and 170° for 4 to 8 hours with liberated water beingremoved during reaction. The Knoevenagel reaction whereinα,β-unsaturated compounds can be prepared by reaction of activemethylene compounds with aldehydes is illustrative. Such reactions takeplace with or without solvent and with or without catalyst. Generally,the reaction takes place at temperatures between about 120° C. and 170°for 4 to 8 hours with liberated water being removed during reaction. Thereaction products are often fractionally distilled to obtained thedesired α,β-unsaturated compound.

[0181] The reaction products are often fractionally distilled toobtained the desired α,β-unsaturated compound.

[0182] Active Methylene Compound

[0183] Active methylene compounds (1) used to prepare (B) theα,β-unsaturated carboxylic compound have the general formula

[0184] wherein each R′ is independently R or OR and each R is,independently, H or a hydrocarbyl group. Useful active methylenecompounds include malonic acid and esters thereof, especially diloweralkyl malonate esters, and acetoacetic acid esters, particularly, loweralkyl, such as methyl, ethyl and propyl acetoacetates.

[0185] Especially preferred di-lower alkyl malonate esters are dimethylmalonate, diethyl malonate and methyl ethyl malonate. Especiallypreferred lower alkyl acetoacetates include methyl- orethyl-acetoacetate.

[0186] Carbonyl Compound

[0187] Carbonyl compounds used to prepare (B) the α,β-unsaturatedcarboxylic compound have the general formula

[0188] wherein R^(a) is H or hydrocarbyl, especially H or lower alkyl,and R^(b) is a member of the group consisting of H, hydrocarbyl and

[0189] wherein each R′ is independently R or OR and each R is,independently, H or a hydrocarbyl group; and lower alkyl acetals,ketals, hemiacetals and hemiketals of the carbonyl compound

[0190] In one embodiment, the carbonyl compound comprises an aldehydewherein R^(a) is H and R^(b) is H or lower alkyl. In another embodiment,the carbonyl compound comprises a ketone wherein each of R^(a) and R^(b)is a lower alkyl group. Formaldehyde is a useful aldehyde. Usefulketones include acetone and methyl ethyl ketone

[0191] In a preferred embodiment the carbonyl compound is a compoundhaving the general formula

[0192] wherein each R′ is independently R or OR and each R is,independently, H or a hydrocarbyl group; or a lower alkyl hemiacetalthereof. Preferably, R′ is a group of the formula OR wherein R isindependently H or lower alkyl.

[0193] Preferred carbonyl compounds are glyoxylic acids and reactiveequivalents thereof. In one preferred embodiment, the carbonyl compoundis glyoxylic acid or the hydrate thereof. Particularly preferred arelower alkyl esters of glyoxylic acid. Especially preferred is a loweralkyl hemiacetal of a lower alkyl glyoxylate, most preferably, themethyl bemiacetal of methyl glyoxylate.

[0194] The following examples illustrate several α,β-unsaturatedcarboxylic compounds used in the preparation of the hydrocarbylsubstituted carboxylic compositions of this invention. In these and inexamples that follow, unless indicated otherwise, all parts are parts byweight, temperatures are in degrees Celsius, and pressures areatmospheric. The relationship between parts by weight and parts byvolume is as grams to milliliters. Filtrations are conducted employing adiatomaceous earth filter aid.

EXAMPLE (B)-1

[0195] A reactor is charged with 30 parts dimethyl malonate and 27.2parts glyoxylic acid methyl ester methyl hemiacetal (hereinafter GMHA).While these are being mixed, 23.17 parts acetic anhydride are added froman addition funnel at ambient temperature. Heating is begun and after0.7 hour the temperature is 105° C. Heating is continued whiledistillate is collected in a Dean-Stark trap. Heating is continued for4.7 hours while the temperature is increased to 130° C. At this point 8parts by volume distillate has been collected in the Dean-Stark trap.The temperature is increased to 160° C. and is maintained for 7.5 hourswhile collecting 8.2 parts by volume additional distillate. Heating at160° C. is continued for 7 hours followed by heating to 200° C. andvacuum distillation at 10 mm Hg pressure. Two fractions are obtained.Yield of desired product is 11.84 parts (25.8%).

EXAMPLE (B)-2

[0196] A reactor is charged with 30 parts dimethyl malonate and 27.2parts GMHA. The materials are heated, under N₂ to 140 ° C. over 1 hourthen temperature is maintained for 1.5 hours while collecting 6 parts byvolume distillate in Dean-Stark trap The temperature is increased to160° C. and is maintained for 13 hours. The temperature is increased to170° C. and the materials are vacuum stripped at 5.2 mm Hg pressure.Solids and clear colorless liquid distill over and 6.48 parts whitesolid is isolated from the liquid by filtration through filter paper.The solid is the product at 14.13% yield.

EXAMPLE (B)-3

[0197] A reactor is charged with 253.73 parts dimethyl malonate and230.65 parts GMHA. The materials are heated, under N₂ to 117° C. then to125° C. over 5 hours while collecting 50 parts by volume distillate in aDean-Stark-trap. The temperature is increased to 130° C. then to 170° C.over 6.5 hours while collecting an additional 36.2 parts distillate. Thetemperature is increased to a maximum of 188° C. at 4.5 mm Hg pressurewhile collecting 199.65 parts distillate (51% yield). The distillate isthe product.

EXAMPLE (B)-4

[0198] A reactor is charged with 132.12 parts dimethyl malonate and120.1 parts GMHA. To the stirring mixture are added 1.79 partsdibutylamine. The materials are heated under N₂, to 130° C. over 8.25hours while collecting a total of 36.5 parts by weight distillate in aDean-Stark trap. The materials are cooled to 110° C. and vacuumdistilled. The fraction collected at 6-10 mm Hg pressure and headtemperature 134-152° C. (93.9 parts, 46.4% yield) is the product.

EXAMPLE (B)-5

[0199] A reactor is charged with 132.12 parts dimethyl malonate and120.1 parts GMHA. The materials are heated, under N₂, over 7 hours whilecollecting a total of 273 parts by volume (235 parts by weight)distillate in a Dean-Stark trap. The temperature is increased to 170° C.and the materials are vacuum distilled. The fraction collected at156-171° C. pot temperature (21-5 mm Hg pressure, 139-170° C. headtemperature) (398.95 parts, 39.5 % yield) is the product.

EXAMPLE (B)-6

[0200] A reactor is charged with 264.24 parts dimethyl malonate, 240.2parts GMHA and 5.49 parts 70% aqueous methane sulfonic acid. Thematerials are heated to 140° C. over 6.25 hours while collecting a totalof 63.8 parts distillate in a Dean-Stark trap. The temperature isincreased to 160° C. and is maintained for 2.5 hours while collecting anadditional 29 parts by volume distillate. The materials are vacuumdistilled collecting 230.68 parts, (57.07% yield) at pot temperature154-162° C., head temperature 130-140° C. and 5.6-30 mm Hg pressure asthe product.

EXAMPLE (B)-7

[0201] A reactor is charged with 132.12 parts dimethyl malonate, 120.01parts GMHA and 0.89 parts β-alanine. The materials are heated, under N₂,to 130° C. while collecting a total of 13.58 parts distillate in aDean-Stark trap. The temperature is increased to 160° C. over 4.5 hoursand is maintained for 2 hours while collecting an additional 11,65 partsdistillate. The materials are vacuum distilled collecting 93.73 parts(46.37% yield) at pot temperature of 134-178° C., head temperature108-120° C. at 4.4-7.5 mm Hg pressure as the product.

EXAMPLE (B)-8

[0202] A reactor is charged with 132.12 parts dimethyl malonate, 120.01parts GMHA and 1.77 parts 30% aqueous NH₁OH. The materials are heated,under N₂, to 151° C. over 3 hours while collecting a total of 30.5 partsdistillate in a Dean-Stark trap. The materials are vacuum distilledcollecting 54.07 parts (26.74% yield) at pot temperature 145-157° C.,head temperature 100-134° C. at 6-7.8 mm Hg pressure as the product.

EXAMPLE (B)-9

[0203] A reactor is charged with 532.3 parts GMHA, 585.6 parts dimethylmalonate and 6.08 parts 70% aqueous methanesulfonic acid. The materialsare heated, under N₂, to 130° C. over 5.5 hours while collecting 43.79parts distillate in a Dean-Stark trap. The temperature is increased to140° C. and is maintained for 1 hour while collecting an additional91.82 parts distillate. The temperature is increased to 150° C. over 1hour and is maintained for 5.5 hours while collecting an additional 84.3parts distillate. To the residue are added 4.62 parts Na₂CO₃, thematerials are filtered then vacuum distilled to 150° C. and 10 mm Hgpressure. The fraction distilling at 100-130° C. (246.01 parts, 27.5 %yield) is collected as the product.

EXAMPLE (B)-10

[0204] A reactor is charged with 720.6 parts GMHA and 660 parts dimethylmalonate. The materials are heated, under N₂, to 120° C. over 6 hours,collecting 81.22 parts distillate in a Dean-Stark trap. The temperatureis increased to 150° C. over 6 hours, collecting an additional 121.93parts distillate. The temperature is maintained for 6 hours, collectingan additional 47.52 parts distillate. The materials are vacuum distilledcollecting 401.69 parts (39.7% yield) at 150-160° C. pot temperature,100-127° C. head temperature at 5 mm Hg pressure as the product.

EXAMPLE (B)-11

[0205] A reactor is charged with 160.17 parts dimethyl malonate and120.1 parts GMHA. The materials are heated under N₂ to 150° C. over 8hours, collecting a total of 43 parts by volume distillate in aDean-Stark trap. The temperature is maintained for 4 hours, collectingan additional 37.8 parts distillate. The materials are vacuum distilled.The fraction distilling 100-120° C. head temperature at 3.3 mm Hgpressure (121.87 parts, 52.9% yield) is collected as product.

EXAMPLE (B)-12

[0206] A reactor is charged with 30 parts dimethyl malonate, 27.2 partsGMHA and 0.62 parts 70% aqueous methanesulfonic acid. The materials areheated to 160° C. over 5 hours then the temperature is maintained for 3hours. The materials are vacuum stripped to 130° C. and 4.9 mm Hg. Thesolid-liquid mixture is obtained. The mixture is filtered through paperand 12,85 parts white solids (28% yield) is collected as the product.

EXAMPLE (B)-13

[0207] A reactor is charged with 240.2 parts GMHA, 264.24 parts dimethylmalonate and 25 parts of sulfonated poly(styrene-co-divinylbenzene)resin (AMBERLYST® 35, Rohm and Haas)). The materials are heated, underN₂, to 120° C. over 7 hours, then maintained at temperature for 13.5hours. The materials are filtered to remove Amberlyst 35, and the liquidfiltrate is vacuum distilled. The fraction distilling at 150° C. pottemperature, 95-125° C. head temperature at 8.3 mm Hg pressure (138.1parts, 34.1% yield, is collected as the product.

EXAMPLE (B)-14

[0208] A reactor is charged with 65.07 parts ethyl acetoacetate, 61.02parts GMHA, 5.0 parts 3-aminopropyl-functionalized silica gel and 100parts by volume toluene. The materials are heated, under N₂, to 70° C.over 0.5 hour, then temperature is maintained for hours. The temperatureis increased to 80° C. over 3.25 hour then to 90° C. over 2 hours. Thetemperature is maintained at 90° C. for 7 hours. The materials arevacuum distilled. The fraction distilling at 130° C. pot temperature,115° C. head temperature at 5.4 mm Hg pressure (55.3 parts, 54.7% yield,is collected as the product. The product is 93.3% triethylethylenetricarboxylate as determined by gas chromatography/MS.

EXAMPLE (B)-15

[0209] A reactor is charged with 300 parts dimethyl malonate and 272.7parts GMHA. The materials are heated, under N₂, to 123° C. at which timea strong reflux is observed. The materials are heated to 170° C. over6.5 hours while 107.1 parts distillate are collected. The residue, 400.9parts, 87.3% yield is the product.

EXAMPLE (B)-16

[0210] The crude liquid product (225 parts) of Example (B)-15 is vacuumdistilled at maximum pot temperature of 200° C. and 4 mm Hg pressure.The distillate, a white solid in a clear liquid (total 148.87 parts) iscollected and is the product.

EXAMPLE (B)-17

[0211] A reactor is charged with 1322.2 parts dimethyl malonate and1201.8 parts GMHA. The materials are heated, under N₂ to 150° C. over 5hours then temperature is maintained for 5 hours. The temperature isincreased to 145° C., is maintained for 1 hour, then is increased to150° C. and is maintained at temperature for 4 hours. A total of 427.38parts distillate is collected. The materials are vacuum distilled,collecting the fraction distilling at 130-150° C./5 mm Hg pressure(477.3 parts, 23.6 % yield).

EXAMPLE (B)-18

[0212] A reactor is charged with 260.28 parts ethyl acetoacetate, 240.2parts GMHA, 20 parts 3-aminopropyl-functionalized silica gel and 400parts by volume toluene. The materials are heated, under N₂, to 90° C.over 1 hour then temperature is maintained at 90° C. for 7.5 hours whileremoving distillate. The materials are filtered through filter paperwhich is subsequently washed with 100 parts by volume toluene. Thefiltrate and washings are vacuum stripped to 110° C. pot temperature(80° C. head temperature) at 3 mm Hg pressure, yielding 367.51 parts(91.78% yield) as the major product.

EXAMPLE (B)-19

[0213] A portion of the product of Example (B)-18 (280 parts) is vacuumdistilled to 135° C. and 4 mm Hg pressure yielding 233.07 partsdistillate as product.

[0214] Hydrocarbyl Group Substituted Carboxylic Compositions

[0215] This invention is also directed to hydrocarbyl group substitutedcarboxylic compositions and a process for preparing said carboxyliccompositions comprising reacting

[0216] (A) a hydrocarbon polymer having {overscore (M)}_(n) ranging fromabout 20,000 to about 500,000, and

[0217] (B) an α,β-unsaturated carboxylic compound prepared by reacting

[0218] (1) an active methylene compound of the formula

[0219] and

[0220] (2) a carbonyl compound of the general formula

[0221] wherein R^(a) is H or hydrocarbyl and R^(b) is a member of thegroup consisting of H, hydrocarbyl and

[0222] wherein each R′ is independently R or OR and each R is,independently, H or a hydrocarbyl group; and lower alkyl acetals,ketals, hemiacetals and hemiketals of the carbonyl compound (2).Preferred reactants for use in the process are the same as thosedescribed hereinabove.

[0223] Reactants (A) and (B) are generally reacted in amounts rangingfrom about 0.95 to about 4 moles (B) per equivalent of (A), wherein anequivalent of (A) is defined as the molecular weight of (A) divided bythe number of olefinic groups therein. For example, the equivalentweight of a EPDM co-polymer having molecular weight of 20,000 andcontaining 4 olefinic groups is 5,000. In one preferred embodiment,about 3 moles (B) are reacted per equivalent of (A), while in anotherpreferred embodiment, about 1 mole (B) is reacted with one equivalent of(A),

[0224] The process may be conducted at ambient pressure, undersuperatmospheric pressure or under reduced pressure Usually, except whenvolatile by-products are being removed from the reaction mixture underreduced pressure, there is usually no advantage to conduct the reactionunder other than ambient pressure.

[0225] When the hydrocarbon polymer is substantially saturated, theprocess is conducted employing free radical conditions.

[0226] Radical grafting is preferably carried out using free radicalinitiators such as peroxides, hydroperoxides, and azo compounds whichdecompose thermally within the grafting temperature range to providesaid free radicals.

[0227] Free radical generating reagents are well know to those skilledin the art. Examples include benzoyl peroxide, t-butyl perbenzoate,t-butyl metachloroperbenzoate, t-butyl peroxide,sec-butylperoxydicarbonate, azobisisobutyronitrile, and the like.Numerous examples of free radical-generating reagents, also known asfree-radical initiators, are mentioned in the above-referenced tests byFlory and by Bovey and Winslow. An extensive listing of free-radicalinitiators appears in J. Brandrup and E. H. Immergut, Editor, “PolymerHandbook”, 2nd edition, John Wiley and Sons, New York (1975), pages II-1to II-40. Preferred free radical-generating reagents include t-butylperoxide, t-butylhydroperoxide, t-butyl perbenzoate, t-amyl peroxide,cumyl peroxide, t-butyl peroctoate, t-butyl-m-chloroperbenzoate andazobisisovaleronitrile.

[0228] The free-radical initiators are generally used in an amount from0.01 to about 10 percent by weight based on the total weight of thereactants. Preferably, the initiators are used at about 0.05 to about 1percent by weight.

[0229] The reaction is usually conducted at temperatures ranging betweenabout 80° C. to about 200° C., preferably between about 130° C. to about170° C. Considerations for determining reaction temperatures includereactivity of the system and the half-life of the initiator at aparticular temperature.

[0230] The choice of free radical generating reagent can be an importantconsideration. For example, when a polymer undergoing grafting with amonomer is diluted with a solvent such as a hydrocarbon oil, grafting ofthe monomer onto the oil diluent may occur. It has been observed thatthe choice of initiator affects the extent of grafting of the monomeronto the oil diluent. Reducing the amount of monomer grafted onto thediluent usually results in an increased amount of monomer grafted ontothe polymer. Improved efficiency of monomer grafting onto substantiallysaturated copolymer resins has been described by Lange et al. in U.S.Pat. No. 5,298,565 which is hereby incorporated herein by reference forrelevant disclosures in this regard.

[0231] When the hydrocarbon polymer is olefinically unsaturated, theprocess may be conducted thermally at temperatures ranging from ambient,usually from at least about 20° C. up to about 250° C., more often fromabout 80° C. to about 220° C.

[0232] In one embodiment, the process is conducted wherein said reactingof (A) the hydrocarbon polymer and (B) the α,β-unsaturated carboxyliccompound is conducted with the addition of from about 0.1 to about 2.5moles Cl₂ per mole of (B) polycarboxylic compound. In anotherembodiment, the reacting is conducted with the addition of from about0.1 to about 2.2 moles Cl₂ per equivalent of olefinically unsaturatedhydrocarbon. The process with added chlorine is also generally conductedat an elevated temperature, typically from about 130° C. up to about200° C.

[0233] The following examples illustrate hydrocarbyl group substitutedcarboxylic compositions of this invention. Temperatures, pressures, andamounts are expressed in terms as set forth hereinabove. Filtrations areconducted employing a diatomaceous earth filter aid.

EXAMPLE 1

[0234] A reactor is charged with 2000 parts of a 14 weight % in mineraloil solution of an ethylene/propylene/dicyclopentadiene copolymer(weight ratio of 63/36/1.5) having {overscore (M)}_(w) 150,000 and anaverage of about 12 C═C per molecule (Uniroyal Chemical). The solutionis heated with stirring to 100° C. under N₂, 10 parts of the product ofExample (B)-5 are added then the temperature is increased to 130° C. Asolution of 5 parts t-butyl peroxybenzoate and 5 parts toluene is addeddropwise over 0.75 hour. The temperature is maintained for 3 hours thenthe materials are cooled whereupon streaks of solid material appeared onreactor walls. Toluene, 200 parts by volume, is added and the materialsare heated to 130° C. whereupon a solution of 2.5 parts t-butylperoxybenzoate and 2.5 parts toluene added over 0.25 hour. The reactionis continued at 130° C. for 3 hours. Upon cooling, a significantlyreduced amount (estimated 1-2 parts) of solids adhere to reactor wall.The materials are vacuum stripped for 0.5 hour at 150° C. and 20 mm Hgpressure. The residue is mixed with 800 parts mineral oil and the oilsolution is collected as the product.

[0235] The hydrocarbyl group substituted carboxylic compositions of thisinvention are useful as additives for lubricating oil compositions andmay be incorporated in a minor amount into a major amount of an oil oflubricating viscosity. They also serve as intermediates to undergofurther reaction with amines, alcohols and metal-containing compounds toprepare derivative compositions which are useful as dispersant viscosityimprovers for lubricants and fuels. The carboxylic derivativecompositions are also incorporated in a minor amount into a major amountof an oil of lubricating viscosity. A major amount is defined herein asany amount greater than 50% by weight and a minor amount is any amountless than 50% by weight provided the total of all components is 100%.

[0236] Hydrocarbyl Group Substituted Carboxylic Derivative Compositions

[0237] The instant invention is also directed to derivatives of thehydrocarbyl substituted carboxylic compositions. These derivatives arehydrocarbyl group substituted carboxylic derivative compositionsprepared by reacting at least one hydrocarbyl group substitutedcarboxylic composition of this invention with a reactant selected fromthe group consisting of (a) amines characterized by the presence withintheir structure of at least one condensable H—N<group, (b) alcohols, (c)reactive metal or reactive metal compounds, and (d) a combination of twoor more of any of (a) through (c), the components of (d) being reactedwith the carboxylic composition simultaneously or sequentially, in anyorder.

[0238] The hydrocarbyl group substituted carboxylic compositions aredescribed in detail hereinabove.

[0239] Amines

[0240] The amines may be monoamines or polyamines, typically polyamines,preferably ethylene amines, amine bottoms or amine condensates. Theamines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic,including aliphatic-substituted cycloaliphatic, aliphatic-substitutedaromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic-substituted heterocyclic, aromatic-substitutedaliphatic, aromatic-substituted cycloaliphatic, aromatic-substitutedheterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted alicyclic, and heterocyclic-substitutedaromatic amines and may be saturated or unsaturated.

[0241] Monoamines useful in this invention generally contain from 1 toabout 24 carbon atoms, preferably 1 to about 12, and more preferably 1to about 6. Examples of primary monoamines useful in the presentinvention include methylamine, propylamine, butylamine,cyclopentylamine, dodecylamine, allylamine, cocoamine and stearylamine.Examples of secondary monoamines include dimethylamine, dipropylamine,dicyclopentylamine, methylbutylamine, etc.

[0242] The monoamine may be an alkanol amine represented by at least oneof the formulae:

H₂N—R′—OH,

[0243] and

[0244] wherein each R₄ is independently a hydrocarbyl group of one toabout 22 carbon atoms or hydroxyhydrocarbyl group of two to about 22carbon atoms, preferably one to about four, and R′ is a divalenthydrocarbyl group of about two to about 18 carbon atoms, preferably twoto about four. The group —R′—OH in such formulae represents thehydroxyhydrocarbyl group. R′ can be an acyclic, alicyclic or aromaticgroup. Typically, R′ is an acyclic straight or branched alkylene groupsuch as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc.group. When two R⁴ groups are present in the same molecule they can bejoined by a direct carbon-to-carbon bond or through a heteroatom (e.g.,oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ringstructure. Examples of such heterocyclic amines include N-(hydroxyllower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines,-thiazolidines and the like. Typically, however, each R⁴ isindependently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.

[0245] Examples of alkanolamines include mono- and di-ethanolamine,ethylethanolamine, monomethylethanolamine, etc.

[0246] The hydroxyamines can also be ether N-(hydroxyhydrocarbyl)amines. These are hydroxy poly(hydrocarbyloxy) analogs of theabove-described hydroxy amines (these analogs also includehydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyhydrocarbyl)amines can be conveniently prepared, for example, by reaction ofepoxides with aforedescribed amines and can be represented by theformulae:

H₂N—(R′O)_(x)—H, and

[0247]

[0248] wherein x is a number from about 2 to about 15 and R₄ and R′ areas described above. R₄ may also be a hydroxypoly (hydrocarbyloxy) group.

[0249] Other useful amines include ether amines of the general formula

R₆OR¹NHR₇

[0250] wherein R₆ is a hydrocarbyl group, preferably an aliphatic group,more preferably an alkyl group, containing from 1 to about 24 carbonatoms, R¹ is a divalent hydrocarbyl group, preferably an alkylene group,containing from two to about 18 carbon atoms, more preferably two toabout 4 carbon atoms and R₇ is H or hydrocarbyl, preferably H oraliphatic, more preferably H or alkyl, more preferably H. When R₇ is notH, then it preferably is alkyl containing from one to about 24 carbonatoms. Especially preferred ether amines are those available under thename SURFAM® produced and marketed by Sea Land Chemical Co., Westlake,Ohio.

[0251] The amine may also be a polyamine. The polyamine may bealiphatic, cycloaliphatic, heterocyclic or aromatic. Examples of usefulpolyamines include alkylene polyamines, hydroxy containing polyamines,polyoxyallcylene polyamines, arylpolyamines, and heterocyclicpolyamines.

[0252] Alkylene polyamines are represented by the formula

[0253] wherein n has an average value between about 1 and about 10,preferably about 2 to about 7, more preferably about 2 to about 5, andthe “Alkylene” group has from 1 to about 10 carbon atoms, preferablyabout 2 to about 6, more preferably about 2 to about 4. R₅ isindependently hydrogen, an aliphatic group or a hydroxy-substituted oramino-substituted aliphatic group of up to about 30 carbon atoms.Preferably R₅ is H or lower alkyl, most preferably, H.

[0254] Alkylene polyamines include methylene-, ethylene-, butylene-,propylene-, pentylene- and other polyamines. Higher homologs and relatedheterocyclic amines such as piperazines and N-amino alkyl-substitutedpiperazines are also included. Specific examples of such polyamines areethylene diamine, diethylene triamine, triethylene tetramine,tris-(2-aminoethyl)amine, propylene diamine,N,N-dimethylaminopropylamine, trimethylene diamine, tripropylenetetramine, tetraethylene pentamine, hexaethylene heptamine,pentaethylenehexamine, aminoethyl piperazine, etc.

[0255] Higher homologs obtained by condensing two or more of theabove-noted alkylene amines are similarly useful as are mixtures of twoor more of the aforedescribed polyamines.

[0256] Ethylene polyamines, such as some of those mentioned above, arepreferred. They are described in detail under the heading “Diamines andHigher Amines” in Kirk Othmer's “Encyclopedia of Chemical Technology”,4th Edition, Vol. 8, pages 74-108, John Wiley and Sons, New York (1993)and in Meinhardt, et al, U.S. Pat. No. 4,234,435, both of which arehereby incorporated herein by reference for disclosure of usefulpolyamines. Such polyamines are most conveniently prepared by thereaction of ethylene dichloride with ammonia or by reaction of anethylene imine with a ring opening reagent such as water, ammonia, etc.These reactions result in the production of a complex mixture ofpolyalkylene polyamines including cyclic condensation products such asthe aforedescribed piperazines. Ethylene polyamine mixtures are useful.

[0257] Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave as residuewhat is often termed “polyamine bottoms”. In general, alkylene polyaminebottoms can be characterized as having less than two, usually less than1% (by weight) material boiling below about 200° C. A typical sample ofsuch ethylene polyamine bottoms obtained from the Dow Chemical Companyof Freeport, Tex., designated “E-100” has a specific gravity at 15.6° C.of 1.0168, % nitrogen of 33.15 and a viscosity at 40° C. of 121centistokes. Gas chromatography analysis shows such a sample containsabout 0.93% “Light Ends” (most probably diethylenetriamine), 0.72%triethylenetetramine, 21.74% tetraethylenepentamine and 76.61%pentaethylene hexamine and higher (by weight). These alkylene polyaminebottoms include cyclic condensation products such as piperazine andhigher analogs of diethylenetriamine, triethylenetetramine and the like.

[0258] Another useful polyamine is a condensation product obtained byreaction of at least one hydroxy alkyl compound with at least onepolyamine reactant containing at least one primary or secondary aminogroup. The hydroxy compounds are preferably polyhydric alcohols andamines. Preferably the hydroxy compounds are polyhydric amines.Polyhydric amines include any of the above-described monoamines reactedwith an alkylene oxide (e.g., ethylene oxide, propylene oxide, butyleneoxide, etc.) having two to about 20 carbon atoms, preferably two toabout four. Examples of polyhydric amines includetri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,2-amino-2-methyl-1,3-propanediol, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and N,N,N′,N′-tetrakis(2-hydroxyethyl) ethylenediamine.

[0259] Polyamine reactants, which react with the polyhydric alcohol oramine to form the condensation products or condensed amines, aredescribed above. Preferred polyamine reactants includetriethylenetetramine (TETA), tetraethylenepentamine (TEPA),pentaethylenehexamine (PEHA), and mixtures of polyamines such as theabove-described “amine bottoms”.

[0260] The condensation reaction of the polyamine reactant with thehydroxy compound is conducted at an elevated temperature, usually about60° C. to about 265° C. in the presence of an acid catalyst.

[0261] The amine condensates and methods of making the same aredescribed in Steckel (U.S. Pat. No. 5,053,152) which is incorporated byreference for its disclosure to the condensates and methods of makingamine condensates.

[0262] The polyamines may be hydroxy-containing polyamines. Theseinclude hydroxy-containing polyamine analogs of hydroxy monoamines,particularly alkoxylated alkylenepolyamines. Such polyamines can be madeby reacting the above-described alkylene amines with one or more of theabove-described alkylene oxides.

[0263] Specific examples of alkoxylated alkylenepolyamines includeN-(2-hydroxyethyl)ethylenediamine,N,N-di-(2-hydroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)piperazine,mono-(hydroxypropyl)-substituted tetraethylenepentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above illustrated hydroxy-containing polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid polyamines arealso useful.

[0264] The polyamines may be polyoxyalkylene polyamines, includingpolyoxyethylene and polyoxypropylene diamines and the polyoxypropylenetriamines having average molecular weights ranging from about 200 toabout 2000. Polyoxyalkylene polyamines, includingpolyoxyethylene-polyoxypropylene polyamines, are commercially available,for example under the tradename JEFFAMINES® from Texaco Chemical Co.U.S. Pat. Nos. 3,804,763 and 3,948,800 contain disclosures ofpolyoxyalkylene polyamines and are incorporated herein by reference fortheir disclosure of such materials.

[0265] In another embodiment, the polyamine may be a heterocyclicpolyamine. The heterocyclic polyamines include aziridines, azetidines,azolidines, tetra- and dihydropyridines, pyrroles, indoles, piperidines,imidazoles, di- and tetrahydroimidazoles, piperazines, isoindoles,purines, N-aminoalkyl-thiomorpholines, N-aminoalkylmorpholines,N-aminoalkyl-piperazines, N,N′-bisaminoalkyl piperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Preferred heterocyclic amines are the saturated 5- and6-membered heterocyclic amines containing only nitrogen, or nitrogenwith oxygen and/or sulfur in the hetero ring, especially thepiperidines, piperazines, thiomorpholines, morpholines, pyrrolidines,and the like. Piperidine, aminoalkylsubstituted piperidines, piperazine,aminoalkylsubstituted piperazines, morpholine, aminoalkylsubstitutedmorpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, areespecially preferred. Usually the aminoalkyl substituents aresubstituted on a nitrogen atom forming part of the hetero ring. Specificexamples of such heterocyclic amines include N-aminopropylmorpholine,N-amino-ethylpiperazine, and N,N′-diaminoethyl-piperazine. Hydroxy alkylsubstituted heterocyclic polyamines are also useful. Examples includeN-hydroxyethylpiperazine and the like.

[0266] Another useful amine is the condensation product of ahydrocarbyl, preferably aliphatic, containing from about 30 to about 200carbon atoms, substituted mono- or polycarboxylic acid with at least oneof the aforementioned polyamines in relative amounts such that theresulting condensation product contains at least one condensable N—Hgroup. The condensation product may be pre-formed condensation or formedin situ. The pre-formed condensation product is preferred. Examplesinclude polyisobutenyl ({overscore (M)}₁˜1000) substituted succinicanhydride-ethylene polyamine and polypropylene ({overscore (M)}_(b)˜800)substituted propionic acid-ethylene polyamine reaction products whereineach contains at least one condensable N—H group.

[0267] Hydrazine and substituted-hydrazine can also be used to formnitrogen-containing carboxylic dispersants. At least one of thenitrogens in the hydrazine must contain a hydrogen directly bondedthereto. Preferably there are at least two hydrogens bonded directly tohydrazine nitrogen and, more preferably, both hydrogens are on the samenitrogen. The substituents which may be present on the hydrazine includealkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, thesubstituents are alkyl, especially lower alkyl, phenyl, and substitutedphenyl such as lower alkoxy-substituted phenyl or loweralkyl-substituted phenyl. Specific examples of substituted hydrazinesare methylhydrazine, N,N-dimethyl-hydrazine, N,N′-dimethylhydrazine,phenylhydrazine, N-phenyl-N′-ethylhydrazine,N-(para-tolyl)-N′-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine,N-(para-nitrophenyl)-N-methyl-hydrazine,N,N′-di(para-chlorophenol)-hydrazine, N-phenyl-N′-cyclohexylhydrazine,amino guanidine bicarbonate, and the like.

[0268] The carboxylic derivative compositions produced by reacting thehydrocarbyl group substituted carboxylic composition of the inventionand the amines described above are acylated amines which include aminesalts, amides, imides and imidazolines as well as mixtures thereof. Toprepare the carboxylic derivative compositions from the amines, one ormore of the hydrocarbyl group substituted carboxylic composition and oneor more amines are heated, optionally in the presence of a normallyliquid, substantially inert organic liquid solvent/diluent, attemperatures in the range of from about 80° C. up to the decompositionpoint of any of the reactants or the product, but normally attemperatures in the range of from about 100° C. up to about 300° C.,provided 300° C. does not exceed the decomposition point. Temperaturesof about 125° C. to about 250° C. are normally used. The carboxyliccomposition and the amine are reacted in an amount sufficient to providefrom about one-half equivalent up to two moles of amine per equivalentof the carboxylic composition. In another embodiment, the carboxyliccomposition is reacted with from about one-half equivalent up to onemole of amine per equivalent of the carboxylic composition. For thepurpose of this invention, an equivalent of amine is that amount ofamine corresponding to the total weight of amine divided by the totalnumber of nitrogens present having at least one H—N<group. Thus, octylamine has an equivalent weight equal to its molecular weight;ethylenediamine has an equivalent weight equal to one-half its molecularweight, and aminoethylpiperazine, with 3 nitrogen atoms but only twohaving at least one H—N<group, has an equivalent weight equal toone-half of its molecular weight.

[0269] Alcohols

[0270] The carboxylic compositions may be reacted with (b) alcohols.Alcohols useful as (b) in preparing carboxylic derivative compositionsof this invention from the hydrocarbyl group substituted carboxyliccomposition previously described include those compounds of the generalformula

R₃—(OH)_(m)

[0271] wherein R₃ is a monovalent or polyvalent organic radical joinedto the —OH groups through carbon-to-oxygen bonds (that is,

—C—OH

[0272] wherein the carbon is not part of a carbonyl group) and m is aninteger of from 1 to about 10, usually 2 to about 6. As with the aminereactant (a), the alcohols can be aliphatic, cycloaliphatic, aromatic,and heterocyclic, including aliphatic-substituted cycloaliphaticalcohols, aliphatic-substituted aromatic alcohols, aliphatic-substitutedheterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substitutedheterocyclic alcohols, heterocyclic-substituted aliphatic alcohols,heterocyclic-substituted cycloaliphatic alcohols, andheterocyclic-substituted aromatic alcohols. Except for polyoxyalkylenealcohols, the mono- and polyhydric alcohols corresponding to the aboveformula will usually contain not more than about 40 carbon atoms andgenerally not more than about 20 carbon atoms. The alcohols may containnon-hydrocarbon substituents of the same type mentioned with respect tothe amines above, that is, non-hydrocarbon substituents which do notinterfere with the reaction of the alcohols with the acylating reagentsof this invention. In general, polyhydric alcohols are preferred.

[0273] The monohydric and polyhydric alcohols useful as (b) includemonohydroxy and polyhydroxy aromatic compounds. Monohydric andpolyhydric phenols and naphthols are preferred hydroxyaromaticcompounds. These hydroxy-substituted aromatic compounds may containother substituents in addition to the hydroxy substituents such as halo,alkyl, alkenyl, alkoxy, alkyl-mercapto, nitro and the like. Usually, thehydroxy aromatic compound will contain 1 to 4 hydroxy groups. Thearomatic hydroxy compounds are illustrated by the following specificexamples: phenol, beta-naphthol, cresols, resorcinol, catechol,carvacrol, thymol, eugenol, p,p′-dihydroxybiphenyl, hydroquinone,pyrogallol, phloroglucinol, orcin, guaicol, 2,4-dibutylphenol,propenetetramer-substituted phenol, didodecylphenol,4,4′-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol,polyisobutenyl-(molecular weight of about 1000)-substituted phenol, thecondensation product of heptylphenol with 0.5 mole of formaldehyde, thecondensation product of octylphenol with acetone,di(hydroxyphenyl)oxide, di(hydroxyphenyl)sulfide,di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol. Phenol itself andaliphatic hydrocarbon-substituted phenols, e.g., alkylated phenolshaving up to 3 aliphatic hydrocarbon substituents are especiallypreferred. Each of the aliphatic hydrocarbon substituents may contain100 or more carbon atoms but usually will have from 1 to 20 carbonatoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbonsubstituents.

[0274] Further specific examples of monohydric alcohols which can beused as (b) include monohydric alcohols such as methanol, ethanol,isooctanol, cyclohexanol, behenyl alcohol, neopentyl alcohol, isobutylalcohol, benzyl alcohol, beta-phenethyl alcohol, 2,-methylcyclohexanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, sec-pentyl alcohol, tert-butyl alcohol, and dioleate ofglycerol. Alcohols within (b) may be unsaturated alcohols such as allylalcohol, cinnamyl alcohol, 1-cyclohexene-3-ol and oleyl alcohol.

[0275] Other specific examples of alcohols useful as (b) are the etheralcohols and amino alcohols including, for example, the oxyalkylene,oxy-arylene-, amino- alkylene-, and aminoarylene-substituted alcoholshaving one or more oxyalkylene, aminoalkylene oramino-aryleneoxy-arylene groups. They are exemplified by CELLOSOLVE®,CARBITOL®, phenoxyethanol, heptylphenyl-(oxypropylene)₆-OH,octyl-(oxyethylene)₃₀-OH phenyl-(oxyoctylene)₂-OH,mono-(heptylphenyl-oxypropylene)-substituted glycerol, poly(styreneoxide), amninoethanol, 3-amino-ethylpentanol, di(hydroxyethyl)amine,p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine,N,N,N′,N′-tetrahydroxy-trimethylenediamine, and the like. The polyhydricalcohols preferably contain from 2 to about 10 hydroxy groups. They areillustrated, for example, by the alkylene glycols and polyoxyalkyleneglycols mentioned above such as ethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, dibutylene glycol, and otheralkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain 2 to about 8 carbon atoms.

[0276] Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used as (b). Thecarbohydrates may be exemplified by glucose, fructose, sucrose,rhamnose, mannose, glyceraldehyde, and galactose.

[0277] Polyhydric alcohols having at least 3 hydroxyl groups, some, butnot all of which have been esterified with an aliphatic monocarboxylicacid having from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful as (b). Further specific examples of such partiallyesterified polyhydric alcohols are the monooleate of sorbitol,distearate of sorbitol, monooleate of glycerol, monostearate ofglycerol, di-dodecanoate of erythritol, and the like.

[0278] A preferred class of alcohols suitable as (b) are thosepolyhydric alcohols containing up to about 12 carbon atoms, andespecially those containing 3 to 10 carbon atoms. This class of alcoholsincludes glycerol, erythritol, pentaerythritol, dipentaerythritol,gluconic acid, glyceraldehyde, glucose, arabinose, heptanediols,hexanetriols, butanetriols, guinic acid,2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol,digitalose, and the like. Aliphatic alcohols containing at least threehydroxyl groups and up to 10 carbon atoms are particularly preferred.

[0279] An especially preferred class of polyhydric alcohols for use as(b) are the polyhydric alkanols containing 3 to 10 carbon atoms andparticularly, those containing 3 to 6 carbon atoms and having at leastthree hydroxyl groups. Such alcohols are exemplified by glycerol,erythritol, pentaerythritol, mannitol, sorbitol,2-hydroxymethyl-2-methyl-1,3-propanediol(trimethylolethane),2-hydroxy-methyl-2-ethyl-1,3-propanediol(trimethylpropane),1,2,4-hexanetriol, and the like.

[0280] From what has been stated above, it is seen that (a) may containalcoholic hydroxy substituents and (b) can contain primary, secondary,or tertiary amino substituents. Thus, amino alcohols can fall into both(a) and (b) provided they contain at least one primary or secondaryamino group. If only tertiary amino groups are present, the aminoalcohol belong only in (b).

[0281] Reactive Metals

[0282] Reactive metals, or reactive metal compounds useful as (c) arethose which will form carboxylic acid metal salts with the hydrocarbylgroup substituted carboxylic composition of this invention and thosewhich will form metal-containing complexes with the carboxylicderivative compositions produced by reacting the hydrocarbyl groupsubstituted carboxylic composition with amines and/or alcohols asdiscussed above.

[0283] Reactive metal compounds useful for preparing metal salts ofhydrocarbyl group substituted carboxylic composition of this inventioninclude those salts containing metals selected from the group consistingof Group I metals, Group II metals, Al, Pb, Sn, Co and Ni. Examples ofcompounds include the oxides, hydroxides, alcoholates, and carbonates ofLi, Na, K, Ca, Ba, Pb, Al, Sn, Ni and others. While reactive metals mayalso be employed, it is generally more convenient, and often moreeconomical to employ the metal salts as reactants. An extensive listingof reactive metal compounds useful for preparing the metal salts of thehydrocarbyl group substituted carboxylic composition is provided in U.S.3,271,310 (LeSuer) which is expressly incorporated herein by reference.

[0284] Reactive metal compounds useful as (c) for the formation ofcomplexes with the reaction products of the acylating reagents of thisinvention and amines are disclosed in U.S. Pat. No. 3,306,908.Complex-forming metal reactants useful as (c) include the nitrates,nitrites, halides, carboxylates, phosphates, phosphites, sulfates,sulfites, carbonates, borates, and oxides of cadmium as well as metalshaving atomic numbers from 24 to 30 (including chromium, manganese,iron, cobalt, nickel, copper and zinc). These metals are the so-calledtransition or coordination metals, i.e., they are capable of formingcomplexes by means of their secondary or coordination valence. Specificexamples of the complex-forming metal compounds useful as the reactantin this invention are cobalt, cobaltous oxide, cobaltous chloride,cobaltic chloride, chromous acetate, chromic acetate, chromic sulfate,chromic hexanoate, manganous acetate, manganous benzoate, manganousnitrate, ferrous acetate, ferric benzoate, ferrous bromide, nickelnitrate, nickel dioleate, nickel stearate, copper (I) acetate, cupricbenzoate, cupric formate, cupric nitrite; zinc benzoate, zinc borate,zinc chromate, cadmium benzoate, cadmium carbonate, cadmium butyrate.Hydrates of the above compounds are especially convenient for use in theprocess of this invention.

[0285] U.S. Pat. No. 3,306,908 is expressly incorporated herein byreference for its discussion of reactive metal compounds suitable forforming such complexes and its disclosure of processes for preparing thecomplexes. Basically, those processes are applicable to the carboxylicderivative compositions of the acylating reagents of this invention withthe amines as described above by substituting, or on an equivalentbasis, the acylating reagents of this invention with the high molecularweight carboxylic acid acylating agents disclosed in U.S. Pat. No.3,306,908. The ratio of equivalents of the acylated amine thus producedand the complex-forming metal reactant remains the same as disclosed inU.S. Pat. No. 3,306,908.

[0286] The following examples illustrate carboxylic derivativecompositions of this invention. Temperatures, pressures, and amounts areas set forth hereinabove.

EXAMPLE A

[0287] A reactor is charged with 2637 parts of the product of Example 1(equivalent weights 65,000/C═C, 21,667/C═O). The materials are heated to150° C. under N₂ whereupon 9.7 parts polyamine bottoms (E-100, Dow) areadded dropwise over 0.5 hour. The materials are reacted for 2 hours at150° C. then vacuum stripped to 150° C. at 20 mm Hg pressure. Theresidue is the product containing 0.134% N, total base number=2.82 andtotal acid number=0.35.

EXAMPLE B

[0288] A reactor is charged with 2200 parts of a 14 weigh % in mineraloil solution of an ethylene/propylene/dicyclopentadiene copolymer(weight ratio 63136/1.5%) having {overscore (M)}_(w) 150,000 and anaverage of about 12 C═C per molecule (Uniroyal Chemical) and 220 partstoluene. While stirring, 11 parts of the product of Example (B)-5 areadded followed by heating to 130° C. under N₂. A solution of 8.8 partseach t-butyl peroxybenzoate and toluene is added over 0.75 hour. Thematerials are heated for 2 hours, then vacuum stripped to 150° C. at 20mm Hg pressure. A portion of the residue is removed from the reactorleaving 2550 parts remaining. To this material are added 450 parts of a50% in oil solution of the reaction product of polyisobutylene({overscore (M)}_(n) 1600) substituted succinic anhydride andpolyethylene polyamine bottoms having total base number about 27, totalacid number about 2 and containing about 1.16% N. The materials areheated to 150° C. under N₂, reacted at 150° C. for 3 hours then vacuumstripped to 150° C. at 20 mm Hg pressure. The residue is the productcontaining 0.169% N and having total acid number=1.34.

[0289] The Oil of Lubricating Viscosity

[0290] The lubricating compositions of this invention employ an oil oflubricating viscosity, including natural or synthetic lubricating oilsand mixtures thereof.

[0291] Natural oils include animal oils and vegetable oils (e.g. castoroil, lard oil) as well as mineral lubricating oils such as liquidpetroleum oils and solvent-treated or acid treated mineral lubricatingoils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types.Oils of lubricating viscosity derived from coal or shale are alsouseful. Synthetic lubricating oils include hydrocarbon oils andhalosubstituted hydrocarbon oils such as polymerized andinterpolymerized olefins, etc. and mixtures thereof, alkylbenzenes,polyphenyl, (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.),alkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs and homologues thereof and the like.

[0292] Alkylene oxide polymers and interpolymers and derivatives thereofwhere their terminal hydroxyl groups have been modified byesterification, etherification, etc., constitute another useful class ofknown synthetic lubricating oils.

[0293] Another suitable class of synthetic lubricating oils that can beused comprises the esters of di- and polycarboxylic acids and those madefrom C₅ to C₂₀ monocarboxylic acids and polyols and polyolethers.

[0294] Other synthetic lubricating oils include liquid esters ofphosphorus-containing acids, polymeric tetrahydrofurans and the like,silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils.

[0295] Unrefined, refined and rerefined oils, either natural orsynthetic (as well as mixtures of two or more of any of these) of thetype disclosed hereinabove can be used in the compositions of thepresent invention. Unrefined oils are those obtained directly fromnatural or synthetic sources without further purification treatment.Refined oils are similar to the unrefined oils except they have beenfurther treated in one or more purification steps to improve one or moreproperties. Refined oils include solvent refined oils, hydrorefinedoils, hydrofinished oils, hydrotreated oils, and oils obtained byhydrocracking and hydroisomerization techniques.

[0296] Rerefined oils are obtained by processes similar to those used toobtain refined oils applied to refined oils which have been already usedin service. Such rerefined oils often are additionally processed bytechniques directed to removal of spent additives and oil breakdownproducts.

[0297] Specific examples of the above-described oils of lubricatingviscosity are given in Chamberlin, III, U.S. Pat. No. 4,326,972,European Patent Publication 107,282, and A. Sequeria, Jr., LubricantBase Oil and Wax Processing, Chapter 6, Marcel Decker, Inc., New York(1994), each of which is hereby incorporated by reference for relevantdisclosures contained therein.

[0298] A basic, brief description of lubricant base oils appears in anarticle by D. V. Brock, “Lubrication Engineering”, Volume 43, pages184-5, March, 1987, which article is expressly incorporated herein byreference for relevant disclosures contained therein.

[0299] The Normally Liquid Fuels

[0300] As indicated hereinabove, the products of this invention may alsobe used as additives for normally liquid fuels.

[0301] The fuels used in the fuel compositions of this invention arewell known to those skilled in the art and usually contain a majorportion of a normally liquid fuel such as hydrocarbonaceous petroleumdistillate fuel (e.g., motor gasoline as defined by ASTM SpecificationsD-439-89 and D-4814-91 and diesel fuel or fuel oil as defined in ASTMSpecifications D-396-90 and D-975-91). Fuels containingnon-hydrocarbonaceous materials such as alcohols, ether, organo-nitrocompounds and the like, are also within the scope of this invention asare liquid fuels derived from vegetable or mineral sources. A range ofalcohol and ether type compounds are described as oxygenates.Oxygenate-containing fuels are described in ASTM D-4814-91. Mixtures ofany of the above-described fuels are useful.

[0302] Particularly preferred fuels are gasoline, that is, a mixture ofhydrocarbons having an ASTM boiling point of 60° C. at the 10%distillation point to about 205° C. at the 90% distillation point,oxygenates, and gasoline-oxygenate blends, all as defined in theaforementioned ASTM Specifications for automotive gasolines. Mostpreferred is gasoline.

[0303] The fuel compositions typically contain from about 0.001% toabout 2% by weight, more often up to about 0.5%, even more often up toabout 0.2% by weight of the additives of this invention.

[0304] The fuel compositions of the present invention may contain otheradditives which are well known to those skilled in the art. These caninclude anti-knock agents such as tetra-alkyl lead compounds, leadscavengers such as halo-alkanes, dyes, antioxidants such as hinderedphenols, rust inhibitors such as alkylated succinic acids and anhydridesand derivatives thereof, bacteriostatic agents, auxiliary dispersantsand detergents, gum inhibitors, fluidizers, metal deactivators,demulsifiers, anti-icing agents and the like. The fuel compositions ofthis invention may be lead-containing or lead-free fuels. Preferred arelead-free fuels.

[0305] Other Additives

[0306] As mentioned, lubricating oil compositions of this invention maycontain other components. The use of such additives is optional and thepresence thereof in the compositions of this invention will depend onthe particular use and level of performance required. Thus the otheradditive may be included or excluded. The compositions may comprise azinc salt of a dithiophosphoric acid. Zinc salts of dithiophosphoricacids are often referred to as zinc dithiophosphates, zincO,O′-dihydrocarbyl dithiophosphates, and other commonly used names. Theyare sometimes referred to by the abbreviation ZDP. One or more zincsalts of dithiophosphoric acids may be present in a minor amount toprovide additional extreme pressure, anti-wear and anti-oxidancyperformance.

[0307] In addition to zinc salts of dithiophosphoric acids discussedhereinabove, other additives that may optionally be used in thelubricating oils of this invention include, for example, auxiliarydetergents and dispersants, viscosity improvers, oxidation inhibitingagents, pour point depressing agents, extreme pressure agents, anti-wearagents, color stabilizers and anti-foam agents. The above-mentioneddispersants and viscosity improvers may be used in addition to thecompositions of this invention.

[0308] Auxiliary extreme pressure agents and corrosion and oxidationinhibiting agents which may be included in the compositions of theinvention are exemplified by chlorinated aliphatic hydrocarbons, organicsulfides and polysulfides, phosphorus esters including dihydrocarbon andtrihydrocarbon phosphites, molybdenum compounds, and the like.

[0309] Auxiliary viscosity improvers (also sometimes referred to asviscosity index improvers or viscosity modifiers) may be included in thecompositions of this invention. Viscosity improvers are usuallypolymers, including polyisobutenes, polymethacrylic acid esters, dienepolymers, polyalkyl styrenes, esterified styrene-maleic anhydridecopolymers, alkenylarene-conjugated diene copolymers and polyolefins.Multifunctional viscosity improvers, other than those of the presentinvention, which also have dispersant and/or antioxidancy properties areknown and may optionally be used in addition to the products of thisinvention. Such products are described in numerous publicationsincluding those mentioned in the Background of the Invention. Each ofthese publications is hereby expressly incorporated by reference.

[0310] Pour point depressants are often included in the lubricating oilsdescribed herein. See for example, page 8 of “Lubricant Additives” by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Company Publisher,Cleveland, Ohio, 1967). Pour point depressants, techniques for theirpreparation and their use are described in U.S. Pat. Nos. 2,387,501;2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,748; 2,721,877;2,721,878; and 3,250,715 which are expressly incorporated by referencefor their relevant disclosures.

[0311] Anti-foam agents used to reduce or prevent the formation ofstable foam include silicones or organic polymers. Examples of these andadditional anti-foam compositions are described in “Foam ControlAgents”, by Henry T. Kerner (Noyes Data Corporation, 1976), pages125-162.

[0312] Detergents and dispersants may be of the ash-producing or ashlesstype. The ash-producing detergents are exemplified by oil solubleneutral and basic salts of alkali or alkaline earth metals with sulfonicacids, carboxylic acids, phenols or organic phosphorus acidscharacterized by a least one direct carbon-to-phosphorus linkage.

[0313] The term “basic salt” is used to designate metal salts whereinthe metal is present in stoichiometrically larger amounts than theorganic acid radical. Basic salts and techniques for preparing and usingthem are well known to those skilled in the art and need not bediscussed in detail here.

[0314] Ashless detergents and dispersants are so-called despite the factthat, depending on its constitution, the detergent or dispersant mayupon combustion yield a nonvolatile residue such as boric oxide orphosphorus pentoxide; however, it does not ordinarily contain metal andtherefore does not yield a metal-containing ash on combustion. Manytypes are known in the art, and are suitable for use in the lubricantsof this invention. The following are illustrative:

[0315] (1) Reaction products of carboxylic acids (or derivativesthereof) containing at least about 34 and preferably at least about 54carbon atoms with nitrogen containing compounds such as amine, organichydroxy compounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these “carboxylic dispersants” are described inBritish Patent number 1,306,529 and in many U.S. patents including thefollowing: 3,163,603 3,381,022 3,542,680 3,184,474 3,399,141 3,567,6373,215,707 3,415,750 3,574,101 3,219,666 3,433,744 3,576,743 3,271,3103,444,170 3,630,904 3,272,746 3,448,048 3,632,510 3,281,357 3,448,0493,632,511 3,306,908 3,451,933 3,697,428 3,311,558 3,454,607 3,725,4413,316,177 3,467,668 4,194,886 3,340,281 3,501,405 4,234,435 3,341,5423,522,179 4,491,527 3,346,493 3,541,012 5,696,060 3,351,552 3,541,6785,696,067 RE 26,433 

[0316] (2) Reaction products of relatively high molecular weightaliphatic or alicyclic halides with amines, preferably polyalkylenepolyamines. These may be characterized as “amine dispersants” andexamples thereof are described for example, in the following U.S.patents: 3,275,554 3,454,555 3,438,757 3,565,804

[0317] (3) Reaction products of alkyl phenols in which the alkyl groupscontains at least about 30 carbon atoms with aldehydes (especiallyformaldehyde) and amines (especially polyalkylene polyamines), which maybe characterized as “Mannich dispersants”. The materials described inthe following U.S. patents are illustrative: 3,413,347 3,725,4803,697,574 3,726,882 3,725,277

[0318] (4) Products obtained by post-treating the carboxylic amine orMannich dispersants with such reagents as urea, thiourea, carbondisulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substitutedsuccinic anhydrides, nitrites, epoxides, boron compounds, phosphoruscompounds or the like, Exemplary materials of this kind are described inthe following U.S. patents: 3,036,003 3,282,955 3,493,520 3,639,2423,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,0933,649,659 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,1113,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,5503,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,591,598 3,704,3083,281,428 3,455,832 3,600,372 3,708,522 4,234,435

[0319] (5) Polymers and copolymers of oil-solubilizing monomers such asdecyl methacrylate, vinyl decyl ether and high molecular weight olefinswith monomers containing polar substituents, e.g., aminoalkyl acrylatesor methacrylates, acrylamides and poly-(oxyethylene)-substitutedacrylates. These may be characterized as “polymeric dispersants” andexamples thereof are disclosed in the following U.S. patents: 3,329,6583,666,730 3,449,250 3,687,849 3,519,565 3,702,300

[0320] The above-noted patents are incorporated by reference herein fortheir disclosures of ashless dispersants.

[0321] The above-illustrated additives may each be present inlubricating compositions at a concentration of as little as 0.001% byweight, usually ranging from about 0.01% to about 20% by weight. In mostinstances, they each contribute from about 0.1% to about 10% by weight,more often up to about 5% by weight.

[0322] Additive Concentrates

[0323] The various compositions and other additives described herein canbe added directly to the lubricant. Preferably, however, they arediluted with a substantially inert, normally liquid organic diluent suchas mineral oil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate. Preferred additive concentrates contain the diluentsreferred to hereinabove. These concentrates usually comprise about 0.1to about 80% by weight of the compositions of this invention and maycontain, in addition, one or more other additives known in the art ordescribed hereinabove. Concentrations such as 15%, 20%, 30% or 50% orhigher may be employed.

[0324] Lubricating Oil Compositions

[0325] The instant invention also relates to lubricating oilcompositions containing the carboxylic compositions of the invention. Asnoted hereinabove, the carboxylic compositions of this invention may beblended directly into an oil or lubricating viscosity or, more often,are incorporated into an additive concentrate containing one or moreother additives which in turn is blended into the oil.

[0326] Lubricant Examples AA-BB

[0327] SAE 15W-40 lubricating oil compositions are prepared by blending0.1 part of a 40% in oil solution of a styrene-maleate copolymerneutralized with aminopropylmorpholine; 6.5 parts of an additiveconcentrate prepared by combining 55.385 parts of a 50% in oil solutionof a polyisobutylene ({overscore (M)}_(n) 1600) substituted succinicanhydride-ethylene polyamine reaction product, 8.05 parts of Zn mixedisopropyl-methyl amyl phosphorodithioate, 3.65 parts sulfurizedbutadiene-butyl acrylate Diels-Alder adduct, 0.23 parts2,5-bis(t-nonyldithio)-1,3,4-thiadiazole (Amoco 158 Amoco), 6.58 partsCa overbased (MR 2.3) sulfurized alkyl phenol, 5.35 parts calciumoverbased (MR 11) alkyl benzene sulfonic acid, 3.67 parts calciumoverbased (MR 2.8) alkyl benzene sulfonic acid, 0.07 parts of a kerosenesolution of a commercial silicone antifoam and sufficient mineral oil tobring the total weight of the additive concentrate to 100 parts; and theindicated amounts of the product of the listed Example, in sufficientmineral oil (Exxon stocks) to prepare 100 parts of lubricant: LubricantAA BB Product of Example: (pbw) A (8.0) B (9.4)

[0328] Lubricant Examples CC and DD

[0329] SAE 15W-40 lubricating oil compositions are prepared by blending0.1 part of a 40% in oil solution of a styrene-maleate copolymerneutralized with aminopropylmorpholine; 13 parts of the additiveconcentrate described in Example AA and BB; and the indicated amounts ofthe product of the listed Example, in sufficient mineral oil (Exxonstocks) to prepare 100 parts of lubricant: Lubricant CC DD Product ofExample: (pbw) A (8.0) B (9.4)

[0330] It is known that some of the materials described above mayinteract in the final formulation, so that the components of the finalformulation may be different from those that are initially added. Forinstance, metal ions (of, e.g., a detergent) can migrate to other acidicsites of other molecules. The products formed thereby, including theproducts formed upon employing the composition of the present inventionin its intended use, may not susceptible of easy description.Nevertheless, all such modifications and reaction products are includedwithin the scope of the present invention; the present inventionencompasses the composition prepared by admixing the componentsdescribed above.

[0331] Each of the documents referred to above is incorporated herein byreference. Except in the examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about”. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.As used herein, the expression “consisting essentially of” permits theinclusion of substances which do not materially affect the basic andnovel characteristics of the composition under consideration.

[0332] While the invention has been explained in relation to itspreferred embodiments, it is to be understood that various modificationsthereof will become apparent to those skilled in the art upon readingthe specification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications that fallwithin the scope of the appended claims.

What is claimed is:
 1. A hydrocarbyl group substituted carboxyliccomposition derived from (A) a hydrocarbon polymer having {overscore(M)}_(n) ranging from about 20,000 to about 500,000 and (B) anα,β-unsaturated carboxylic compound prepared by reacting (1) an activemethylene compound of the formula

and (2) a carbonyl compound of the general formula

wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the groupconsisting of H, hydrocarbyl and

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals andhemiketals of the carbonyl compound (2).
 2. The carboxylic compositionof claim 1 wherein the hydrocarbon polymer has {overscore (M)}_(n)ranging from about 40,000 to about 200,000.
 3. The carboxyliccomposition of claim 1 wherein the hydrocarbon polymer is substantiallysaturated.
 4. The carboxylic composition of claim 1 wherein thehydrocarbon polymer contains olefinic unsaturation in the range of fromabout 1 to about 100 C═C bonds per mole of polymer, based on {overscore(M)}_(n).
 5. The carboxylic composition of claim 1 wherein thehydrocarbon polymer comprises a polyolefin.
 6. The carboxyliccomposition of claim 5 wherein the polyolefin comprises anethylene-C₃₋₂₈ olefin copolymer.
 7. The carboxylic composition of claim6 wherein the polyolefin comprises an ethylene-propylene copolymer. 8.The carboxylic composition of claim 1 wherein the hydrocarbon polymercomprises an olefin-polyene copolymer.
 9. The carboxylic composition ofclaim 8 wherein the olefin-polyene polymer comprises an ethylene-C₃₋₂₈olefin-polyene copolymer.
 10. The carboxylic composition of claim 9wherein the polymer comprises an ethylene-propylene-diene copolymer. 11.The carboxylic composition of claim 11 wherein the diene is anon-conjugated diene.
 12. The carboxylic composition of claim 1 whereinthe active methylene compound comprises a di-lower alkyl malonate. 13.The carboxylic composition of claim 1 wherein the active methylenecompound comprises a lower alkyl acetoacetate.
 14. The carboxyliccomposition of claim 12 wherein the di-lower alkyl malonate comprisesdimethyl malonate, diethyl malonate or methyl ethyl malonate.
 15. Thecarboxylic composition of claim 13 wherein the lower alkyl acetoacetatecomprises methyl- or ethyl-acetoacetate.
 16. The carboxylic compositionof claim 1 wherein the carbonyl compound (2) comprises an aldehydewherein R^(a) is H and R^(b) is H or lower alkyl.
 17. The carboxyliccomposition of claim 1 wherein the carbonyl compound (2) comprises aketone wherein each of R^(a) and R^(b) is a lower alkyl group.
 18. Thecarboxylic composition of claim 16 wherein the aldehyde is formaldehyde.19. The carboxylic composition of claim 1 wherein the carbonyl compoundis a compound having the general formula

or a lower alkyl hemiacetal thereof.
 20. The carboxylic composition ofclaim 19 wherein R′ is a group of the formula OR wherein R isindependently H or lower alkyl.
 21. The carboxylic composition of claim26 wherein the carbonyl compound is glyoxylic acid or the hydratethereof.
 22. The carboxylic composition of claim 20 wherein the carbonylcompound is a lower alkyl ester of glyoxylic acid.
 23. The carboxyliccomposition of claim 20 wherein the carbonyl compound is a lower alkylhemiacetal of a lower alkyl glyoxylate.
 24. The carboxylic compositionof claim 23 wherein the carbonyl compound is the methyl hemiacetal ofmethyl glyoxylate,
 25. A hydrocarbyl group substituted polycarboxyliccomposition derived from (A) a hydrocarbon polymer having {overscore(M)}_(n) ranging from about 20,000 to about 500,000 and (B) anα,β-unsaturated polycarboxylic compound prepared by reacting glyoxylicacid or a reactive equivalent thereof with an active methylene compoundof the formula

wherein R′ is selected from R and OR and each R is, independently, H orlower alkyl.
 26. A hydrocarbyl group substituted polycarboxyliccomposition derived from (A) a hydrocarbon polymer having {overscore(M)}_(n) ranging from about 20,000 to about 500,000 and (B) anα,β-unsaturated polycarboxylic compound of the general formula

wherein R^(c) is R;

or —CHO; and each R is, independently, H or hydrocarbyl.
 27. Thecarboxylic composition of claim 26 wherein the polycarboxylic compound(B) is tri(lower alkyl) ethylenetricarboxylate.
 28. A process forpreparing a hydrocarbyl group substituted carboxylic compositioncomprising reacting (A) a hydrocarbon polymer having {overscore (M)}_(n)ranging from about 20,000 to about 500,000 and, (B) an α,β-unsaturatedcarboxylic compound prepared by reacting (1) an active methylenecompound of the formula

and (2) a carbonyl compound of the general formula

wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the groupconsisting of H, hydrocarbyl and

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals andhemiketals of the carbonyl compound (2).
 29. The process of claim 28wherein the hydrocarbon polymer has {overscore (M)}_(n) ranging fromabout 40,000 to about 200,000.
 30. The carboxylic composition of claim28 wherein the hydrocarbon polymer is substantially saturated.
 31. Thecarboxylic composition of claim 28 wherein the hydrocarbon polymercontains olefinic unsaturation in the range of from about 1 to about 100C═C bonds per equivalent, based on {overscore (M)}_(n), of polymer. 32.The carboxylic composition of claim 28 wherein the hydrocarbon polymercomprises a polyolefin.
 33. The carboxylic composition of claim 32wherein the polyolefin comprises an ethylene-C₃₋₂₈ olefin copolymer. 34.The carboxylic composition of claim 33 wherein the polyolefin comprisesan ethylene-propylene copolymer.
 35. The carboxylic composition of claim28 wherein the hydrocarbon polymer comprises an olefin-polyenecopolymer.
 36. The carboxylic composition of claim 35 wherein theolefin-polyene polymer comprises an ethylene-C₃₋₂₈ olefin-polyenecopolymer.
 37. The carboxylic composition of claim 36 wherein thepolymer comprises an ethylene-propylene-diene copolymer.
 38. Thecarboxylic composition of claim 37 wherein the diene is a non conjugateddiene.
 39. The process of claim 28 wherein said reacting of (A) thehydrocarbon polymer and (B) the α,β-unsaturated carboxylic compound isconducted thermally at temperatures ranging from about 20° C. to about250° C.
 40. The process of claim 29 wherein said reacting is conductedat temperatures ranging from about 80° C. to about 220° C.
 41. Theprocess of claim 28 wherein said reacting of is conducted with theaddition of from about 0.1 to about 2.5 moles Cl₂ per mole of (B)polycarboxylic compound.
 42. The process of claim 28 wherein saidreacting conducted with the addition of from about 0.1 to about 2.2moles Cl₂ per equivalent of olefinically unsaturated hydrocarbon. 43.The process of claim 28 wherein the carbonyl compound (2) is glyoxylicacid or a reactive equivalent thereof
 44. The process of claim 28wherein(B) the α,β-unsaturated carboxylic compound is a polycarboxyliccompound of the general formula

wherein R^(c) is R;

or —CHO; and each R is, independently, H or hydrocarbyl.
 45. Ahydrocarbyl group substituted carboxylic composition prepared by theprocess of claim
 28. 46. A lubricating oil composition comprising amajor amount of an oil of lubricating viscosity and a minor amount ofthe hydrocarbyl group substituted carboxylic composition of claim
 1. 47.A lubricating oil composition comprising a major amount of an oil oflubricating viscosity and a minor amount of the hydrocarbyl groupsubstituted carboxylic composition of claim
 45. 48. A hydrocarbyl groupsubstituted carboxylic derivative composition prepared by reacting atleast one hydrocarbyl group substituted carboxylic composition accordingto claim 1 with a reactant selected from the group consisting of (a)amines characterized by the presence within their structure of at leastone condensable H—N<group, (b) alcohols, (c) reactive metal or reactivemetal compounds, and (d) a combination of two or more of any of (a)through (c), the components of (d) being reacted with the carboxyliccomposition simultaneously or sequentially, in any order.
 49. Thecarboxylic derivative composition of claim 48 wherein the carboxyliccomposition is reacted with (a) an amine.
 50. The carboxylic derivativecomposition of claim 49 wherein the carboxylic composition is reactedwith from about 0.5 equivalent up to 1 mole of (a) the amine perequivalent of carboxylic composition.
 51. The carboxylic derivativecomposition of claim 49 wherein (a) the amine is characterized by thegeneral formula

wherein n has an average value between about 1 and about 10, the“Alkylene” group has from 1 to about 10 carbon atoms, and R₅ isindependently hydrogen, an aliphatic group, an amino substitutedaliphatic group or a hydroxy-substituted aliphatic group of up to about30 carbon atoms.
 52. The carboxylic derivative composition of claim 49wherein (a) the amine is a condensed polyamine obtained by the reactionof at least one polyamine containing at least one primary or secondaryamino group with at least one hydroxyalkyl compound.
 53. The carboxylicderivative composition of claim 49 wherein the carboxylic composition isreacted with (b) an alcohol.
 54. A hydrocarbyl group substitutedpolycarboxylic derivative composition prepared by reacting at least onecarboxylic composition of claim 25 with from about 0.5 equivalent up to1 mole of (a) amine per equivalent of carboxylic composition.
 55. Ahydrocarbyl group substituted polycarboxylic derivative compositionprepared by reacting at least one carboxylic composition of claim 26with from about 0.5 equivalent up to 1 mole of (a) amine per equivalentof carboxylic composition.
 56. A process for preparing a hydrocarbylgroup substituted carboxylic derivative composition comprising reactingthe hydrocarbyl substituted carboxylic composition prepared by reacting(A) a hydrocarbon polymer having {overscore (M)}_(n) ranging from about20,000 to about 500,000 and, (B) an α,β-unsaturated carboxylic compoundprepared by reacting (1) an active methylene compound of the formula

and (2) a carbonyl compound of the general formula

wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the groupconsisting of H, hydrocarbyl and

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals andhemiketals of the carbonyl compound (2) with a reactant selected fromthe group consisting of (a) amines characterized by the presence withintheir structure of at least one condensable H—N<group, (b) alcohols, (c)reactive metal or reactive metal compounds, and (d) a combination of twoor more of any of (a) through (c), the components of (d) being reactedwith the carboxylic composition simultaneously or sequentially, in anyorder.
 57. A hydrocarbyl group substituted carboxylic derivativecomposition prepared by the process of claim
 56. 58. An additiveconcentrate for preparing lubricating oil and fuel compositionscomprising from about 20% to about 99% by weight of a normally liquid,substantially inert organic diluent and from about 1% to about 80% byweight of at least one carboxylic composition of claim
 1. 59. Anadditive concentrate for preparing lubricating oil and fuel compositionscomprising from about 20% to about 99% by weight of a normally liquid,substantially inert organic diluent and from about 1% to about 80% byweight of at least one carboxylic derivative composition of claim 48.60. A lubricating oil composition comprising a major amount of an oil oflubricating viscosity and a minor amount of the carboxylic derivativecomposition of claim
 48. 61. A lubricating oil composition comprising amajor amount of an oil of lubricating viscosity and a minor amount ofthe carboxylic derivative composition of claim
 57. 62. A fuelcomposition comprising a major amount of a normally liquid fuel and aminor amount of the carboxylic derivative composition of claim 48.